WO2022202907A1 - Photosensitive resin composition, resin film, and electronic device - Google Patents
Photosensitive resin composition, resin film, and electronic device Download PDFInfo
- Publication number
- WO2022202907A1 WO2022202907A1 PCT/JP2022/013565 JP2022013565W WO2022202907A1 WO 2022202907 A1 WO2022202907 A1 WO 2022202907A1 JP 2022013565 W JP2022013565 W JP 2022013565W WO 2022202907 A1 WO2022202907 A1 WO 2022202907A1
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- Prior art keywords
- group
- resin composition
- compound
- photosensitive resin
- resins
- Prior art date
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- 229920005989 resin Polymers 0.000 title claims abstract description 117
- 239000011347 resin Substances 0.000 title claims abstract description 117
- 239000011342 resin composition Substances 0.000 title claims abstract description 93
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- 229920001721 polyimide Polymers 0.000 claims abstract description 37
- 239000009719 polyimide resin Substances 0.000 claims abstract description 33
- 239000002243 precursor Substances 0.000 claims abstract description 20
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- 125000003647 acryloyl group Chemical group O=C([*])C([H])=C([H])[H] 0.000 claims abstract description 13
- 125000000623 heterocyclic group Chemical group 0.000 claims abstract description 13
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- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 claims abstract description 10
- 125000003700 epoxy group Chemical group 0.000 claims abstract description 9
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- 125000004432 carbon atom Chemical group C* 0.000 claims description 17
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 14
- 125000000217 alkyl group Chemical group 0.000 claims description 8
- 125000005843 halogen group Chemical group 0.000 claims description 7
- 150000003536 tetrazoles Chemical group 0.000 claims description 7
- 150000003852 triazoles Chemical group 0.000 claims description 5
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 4
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- 238000001035 drying Methods 0.000 description 16
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- VEUMBMHMMCOFAG-UHFFFAOYSA-N 2,3-dihydrooxadiazole Chemical compound N1NC=CO1 VEUMBMHMMCOFAG-UHFFFAOYSA-N 0.000 description 2
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- VVBLNCFGVYUYGU-UHFFFAOYSA-N 4,4'-Bis(dimethylamino)benzophenone Chemical compound C1=CC(N(C)C)=CC=C1C(=O)C1=CC=C(N(C)C)C=C1 VVBLNCFGVYUYGU-UHFFFAOYSA-N 0.000 description 2
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- 230000009257 reactivity Effects 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 125000000547 substituted alkyl group Chemical group 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 230000008961 swelling Effects 0.000 description 1
- XSOKHXFFCGXDJZ-UHFFFAOYSA-N telluride(2-) Chemical compound [Te-2] XSOKHXFFCGXDJZ-UHFFFAOYSA-N 0.000 description 1
- GJBRNHKUVLOCEB-UHFFFAOYSA-N tert-butyl benzenecarboperoxoate Chemical compound CC(C)(C)OOC(=O)C1=CC=CC=C1 GJBRNHKUVLOCEB-UHFFFAOYSA-N 0.000 description 1
- CIHOLLKRGTVIJN-UHFFFAOYSA-N tert‐butyl hydroperoxide Chemical compound CC(C)(C)OO CIHOLLKRGTVIJN-UHFFFAOYSA-N 0.000 description 1
- BRKFQVAOMSWFDU-UHFFFAOYSA-M tetraphenylphosphanium;bromide Chemical compound [Br-].C1=CC=CC=C1[P+](C=1C=CC=CC=1)(C=1C=CC=CC=1)C1=CC=CC=C1 BRKFQVAOMSWFDU-UHFFFAOYSA-M 0.000 description 1
- USFPINLPPFWTJW-UHFFFAOYSA-N tetraphenylphosphonium Chemical compound C1=CC=CC=C1[P+](C=1C=CC=CC=1)(C=1C=CC=CC=1)C1=CC=CC=C1 USFPINLPPFWTJW-UHFFFAOYSA-N 0.000 description 1
- 230000000930 thermomechanical effect Effects 0.000 description 1
- 229920001187 thermosetting polymer Polymers 0.000 description 1
- 125000000101 thioether group Chemical group 0.000 description 1
- 125000003396 thiol group Chemical group [H]S* 0.000 description 1
- YRHRIQCWCFGUEQ-UHFFFAOYSA-N thioxanthen-9-one Chemical compound C1=CC=C2C(=O)C3=CC=CC=C3SC2=C1 YRHRIQCWCFGUEQ-UHFFFAOYSA-N 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- IMFACGCPASFAPR-UHFFFAOYSA-N tributylamine Chemical compound CCCCN(CCCC)CCCC IMFACGCPASFAPR-UHFFFAOYSA-N 0.000 description 1
- 125000003866 trichloromethyl group Chemical group ClC(Cl)(Cl)* 0.000 description 1
- 125000002023 trifluoromethyl group Chemical group FC(F)(F)* 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
- 150000003739 xylenols Chemical class 0.000 description 1
- 125000006839 xylylene group Chemical group 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/16—Nitrogen-containing compounds
- C08K5/34—Heterocyclic compounds having nitrogen in the ring
- C08K5/3467—Heterocyclic compounds having nitrogen in the ring having more than two nitrogen atoms in the ring
- C08K5/3472—Five-membered rings
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L101/00—Compositions of unspecified macromolecular compounds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L45/00—Compositions of homopolymers or copolymers of compounds having no unsaturated aliphatic radicals in side chain, and having one or more carbon-to-carbon double bonds in a carbocyclic or in a heterocyclic ring system; Compositions of derivatives of such polymers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L61/00—Compositions of condensation polymers of aldehydes or ketones; Compositions of derivatives of such polymers
- C08L61/04—Condensation polymers of aldehydes or ketones with phenols only
- C08L61/06—Condensation polymers of aldehydes or ketones with phenols only of aldehydes with phenols
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L79/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen with or without oxygen or carbon only, not provided for in groups C08L61/00 - C08L77/00
- C08L79/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L79/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen with or without oxygen or carbon only, not provided for in groups C08L61/00 - C08L77/00
- C08L79/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
- C08L79/08—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
- G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
- G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
- G03F7/032—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with binders
- G03F7/037—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with binders the binders being polyamides or polyimides
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
- G03F7/038—Macromolecular compounds which are rendered insoluble or differentially wettable
Definitions
- the present invention relates to a photosensitive resin composition, a resin film and an electronic device.
- photosensitive resin compositions containing polyamide resins and/or polyimide resins are sometimes used to form cured films such as insulating layers. Therefore, photosensitive resin compositions containing polyamide resins and/or polyimide resins have been investigated.
- US Pat. No. 5,300,002 discloses at least one fully imidized polyimide polymer having a weight average molecular weight ranging from about 20,000 Daltons to about 70,000 Daltons; at least one solubility-switching compound; at least one A photosensitive composition is described which comprises a photoinitiator; and at least one solvent and is capable of forming a film exhibiting a dissolution rate of greater than about 0.15 ⁇ m/sec when cyclopentanone is used as a developer. ing.
- Patent Documents 2, 3, 4, etc. also describe photosensitive resin compositions containing polyamide resins and/or polyimide resins.
- the photosensitive resin composition When forming a cured film in an electronic device using a photosensitive resin composition, first, the photosensitive resin composition is applied onto a substrate to form a film, and the film is patterned by exposure and development. Then, a cured film is formed by heat-treating the patterned film. In the formation of the cured film as described above, it is preferable that the adhesion between the photosensitive resin composition and the substrate is high. In particular, in recent years, there has been a demand for forming a flat cured film on a base material having steps, so there is a further demand for improved adhesion between the photosensitive resin composition and the base material.
- An object of the present invention is to provide a photosensitive resin composition having good adhesion to a substrate.
- a photosensitive resin composition comprising:
- a resin film comprising a cured product of the above photosensitive resin composition is provided.
- An electronic device comprising the above resin film is provided.
- a photosensitive resin composition having good adhesion to a substrate is provided.
- X to Y in the description of numerical ranges means X or more and Y or less, unless otherwise specified.
- “1 to 5% by mass” means “1% by mass or more and 5% by mass or less”.
- alkyl group includes not only alkyl groups without substituents (unsubstituted alkyl groups) but also alkyl groups with substituents (substituted alkyl groups).
- (meth)acryl used herein represents a concept that includes both acryl and methacryl.
- organic group as used herein means an atomic group obtained by removing one or more hydrogen atoms from an organic compound, unless otherwise specified.
- a "monovalent organic group” represents an atomic group obtained by removing one hydrogen atom from an arbitrary organic compound.
- electronic device refers to elements to which electronic engineering technology is applied, such as semiconductor chips, semiconductor elements, printed wiring boards, electric circuit display devices, information communication terminals, light-emitting diodes, physical batteries, and chemical batteries. , devices, final products, etc.
- the photosensitive resin composition of the present embodiment includes at least one or more resins selected from the group consisting of polyimide resins and their precursors, polybenzoxazole resins and their precursors, polyamide resins, novolak resins, and cycloolefin resins ( A) and a compound (C) having at least one or more reactive groups selected from the group consisting of epoxy groups and (meth)acryloyl groups and a 5-membered nitrogen-containing heterocyclic group.
- a cured film in an electronic device is required to have adhesion to a substrate.
- a cured film formed from the photosensitive resin composition of the present embodiment has good adhesion to a metal substrate.
- the details are unknown, it is believed that the interaction between the nitrogen-containing heterocycle of the compound (C) and the substrate surface contributes to the improvement of the adhesion between the cured film and the substrate.
- the compound (C) has a reactive group selected from an epoxy group and a (meth)acryloyl group, the compound (C) reacts with other components contained in the resin composition, or the compound (C ), and the compound (C) becomes closely entangled with the resin composition. It is believed that this further improves the adhesion between the cured film and the substrate.
- the photosensitive resin composition of the present embodiment is preferably used for forming insulating layers in electronic devices.
- the photosensitive resin composition of the present embodiment includes one or more resins selected from the group consisting of polyimide resins and their precursors, polybenzoxazole resins and their precursors, polyamide resins, novolac resins, and cycloolefin resins ( A).
- the photosensitive resin composition of the present embodiment may contain only one resin (A), or may contain two or more resins (A).
- the content of the resin (A) in the photosensitive resin composition of the present embodiment is preferably 1% by mass or more, more preferably 5% by mass or more, more preferably 5% by mass or more, based on the total solid content of the photosensitive resin composition. is 10% by mass or more.
- the upper limit of resin (A) is not particularly limited, but is usually 60% by mass or less, preferably 50% by mass or less.
- the photosensitive resin composition of the present embodiment preferably contains a polyimide resin as the resin (A).
- polyimide resin When using a polyimide resin, only one polyimide resin may be used, or two or more polyimide resins may be used together.
- the conversion rate is preferably 90% or higher, more preferably 95% or higher, and still more preferably 98% or higher.
- the polyimide resin preferably has no or little amide structure and many imide ring structures.
- the imide cyclization rate can be known, for example, from the area of the peak corresponding to the amide group and the area of the peak corresponding to the imide ring group in the NMR spectrum.
- the imide cyclization rate can be known from the area of the peak corresponding to the amide group, the area of the peak corresponding to the imide ring group, and the like in the infrared absorption spectrum.
- the polyimide resin preferably contains a structural unit represented by the following general formula (PI-1).
- X is a divalent organic group
- Y is a tetravalent organic group
- At least one of X and Y is a fluorine atom-containing group.
- the divalent organic group of X and/or the tetravalent organic group of Y preferably contains an aromatic ring structure, more preferably a benzene ring structure. This tends to further increase the heat resistance. From the viewpoint of solubility in organic solvents, both X and Y are preferably fluorine atom-containing groups.
- the divalent organic group of X and/or the tetravalent organic group of Y preferably has a structure in which 2 to 6 benzene rings are linked via a single bond or a divalent linking group. Examples of the divalent linking group here include an alkylene group, a fluorinated alkylene group, an ether group, and the like.
- Alkylene groups and fluorinated alkylene groups may be linear or branched.
- the number of carbon atoms in the divalent organic group of X is, for example, 6-30.
- the number of carbon atoms in the tetravalent organic group of Y is, for example, 6-20.
- Each of the two imide rings in general formula (PI-1) is preferably a 5-membered ring.
- the polyimide resin more preferably contains a structural unit represented by the following general formula (PI-2).
- X is synonymous with X in the general formula (PI-1), Y' represents a single bond or an alkylene group.
- the alkylene group of Y' may be linear or branched. Some or all of the hydrogen atoms in the alkylene group of Y' are preferably substituted with fluorine atoms.
- the number of carbon atoms in the alkylene group of Y' is, for example, 1-6, preferably 1-4, more preferably 1-3.
- a polyimide resin can be obtained by subjecting a polyimide resin precursor to a ring closure reaction.
- a polyamide resin can be used as the polyimide precursor.
- the weight average molecular weight of the polyimide resin and/or polyimide resin precursor is, for example, 5,000 to 100,000, preferably 7,000 to 75,000, and more preferably 10,000 to 50,000.
- the weight average molecular weight of the polyimide resin and/or the polyimide resin precursor is large to some extent, for example, sufficient heat resistance of the cured film can be obtained.
- the weight average molecular weight of the polyimide resin and/or the polyimide resin precursor is not too large, the polyimide resin and/or the polyimide resin precursor can be easily dissolved in the organic solvent.
- the weight average molecular weight can usually be determined by gel permeation chromatography (GPC) using polystyrene as a standard substance.
- polybenzoxazole resin preferably contains a structural unit represented by the following general formula (PB01).
- a polybenzoxazole resin can be obtained by subjecting a polybenzoxazole resin precursor to a ring-closure reaction.
- a polyamide resin can be used as the polybenzoxazole resin precursor.
- polyamide resin The polyamide resin preferably contains a structural unit represented by general formula (PA-1) below.
- polyamide resin When a polyamide resin is used, only one polyamide resin may be used, or two or more polyamide resins may be used together.
- X is a divalent organic group
- Y is a tetravalent organic group
- at least one of X and Y is preferably a fluorine atom-containing group.
- both X and Y in general formula (PA-1) are preferably fluorine atom-containing groups.
- the divalent organic group of X and/or the tetravalent organic group of Y preferably contains an aromatic ring structure, more preferably a benzene ring structure. This tends to further increase the heat resistance.
- the benzene ring here may be substituted with a fluorine atom-containing group such as a fluorine atom or a fluorinated alkyl group (preferably a trifluoromethyl group), or may be substituted with other groups.
- the divalent organic group for X and/or the tetravalent organic group for Y in general formula (PA-1) preferably has 2 to 6 benzene rings via a single bond or a divalent linking group. It has a combined structure.
- Examples of the divalent linking group here include an alkylene group, a fluorinated alkylene group, an ether group, and the like. Alkylene groups and fluorinated alkylene groups may be linear or branched.
- the number of carbon atoms in the divalent organic group of X is, for example, 6-30.
- the tetravalent organic group of Y has, for example, 6 to 20 carbon atoms.
- the polyamide resin more preferably contains a structural unit represented by the following general formula (PA-2).
- X is synonymous with X in the general formula (PA-1), Y' represents a single bond or an alkylene group.
- the polyamide resin can also be used as a polyimide resin precursor or a polybenzoxazole resin precursor.
- the novolak resin can be appropriately selected according to the application as long as it is a resin obtained by reacting phenols and aldehydes in the absence of a catalyst or in the presence of an acidic catalyst or the like.
- a random novolak type or a high ortho novolac type can be used.
- novolak resin When using a novolak resin, only one novolak resin may be used, or two or more novolak resins may be used in combination.
- the novolak resin can be obtained by reacting the aldehydes to the phenols at a molar ratio (aldehydes/phenols) of 0.5 to 1.0.
- phenols used in preparing novolak resins include phenol, o-cresol, m-cresol, p-cresol, xylenol, alkylphenols, catechol, and resorcinol. These phenols may be used singly or in combination of two or more.
- Aldehydes used in preparing the novolac resin include, for example, aldehyde compounds such as formaldehyde, paraformaldehyde, and benzaldehyde, substances that are sources of these aldehyde compounds, and solutions of these aldehyde compounds. can be used. These aldehydes may be used alone or in combination of two or more.
- cycloolefin resin As the cycloolefin resin, general resins having a cycloolefin structure can be appropriately used.
- cycloolefin resin When using a cycloolefin resin, only one cycloolefin resin may be used, or two or more cycloolefin resins may be used in combination.
- the cycloolefin-based resin preferably contains a structural unit derived from a monomer having a cycloolefin structure described below. More preferably, it contains a structural unit derived from a monomer having a cyclic acid anhydride structure described below.
- Structural units derived from monomers having a cycloolefin structure are preferably structural units derived from norbornene-based monomers represented by the following general formula (a1).
- R 6 , R 7 , R 8 and R 9 are each independently hydrogen, a halogen atom or an organic group having 1 to 30 carbon atoms, and n is 0, 1 or 2.
- R 6 to R 9 in general formula (a1) can be, for example, each independently hydrogen, a halogen atom, or an organic group having 1 to 30 carbon atoms.
- R 6 to R 9 are preferably each independently hydrogen, halogen atoms or organic groups having 1 to 10 carbon atoms, more preferably each independently hydrogen, halogen atoms or 1 to 3 carbon atoms and more preferably each independently a hydrogen atom, a halogen atom, or an organic group having 1 carbon atoms.
- the organic group (for example, an organic group having 1 to 30 carbon atoms) constituting R 6 to R 9 may contain one or more atoms selected from O, N, S, P and Si in its structure. . Any two of R 6 to R 9 may combine with each other to form an alkylidene group or a monocyclic or polycyclic structure.
- the photosensitive resin composition of the present embodiment is a compound (C) having at least one or more reactive groups selected from the group consisting of epoxy groups and (meth)acryloyl groups, and a 5-membered nitrogen-containing heterocyclic group.
- the photosensitive resin composition of the present embodiment may contain only one type of compound (C), or may contain two or more types.
- the adhesion between the photosensitive resin composition and the substrate tends to be improved.
- the interaction between the nitrogen-containing heterocycle of the compound (C) and the surface of the substrate contributes to the improvement of adhesion between the cured film and the substrate.
- the compound (C) has a reactive group selected from an epoxy group and a (meth)acryloyl group, the compound (C) reacts with other components contained in the resin composition, or the compound (C ), and the compound (C) becomes closely entangled with the resin composition. It is believed that this further improves the adhesion between the cured film and the substrate.
- the photosensitive resin composition of the present embodiment can be , the adhesiveness to substrates having copper on the substrate surface tends to be particularly excellent.
- the compound (C) is preferably a compound having at least one group selected from the group consisting of a triazole group and a tetrazole group as a five-membered nitrogen-containing heterocyclic group.
- a triazole group is a heterocyclic group containing three nitrogen atoms in a five-membered ring. There are two isomers with different positions of nitrogen atoms, which are called 1,2,3-triazole group and 1,2,4-triazole group, respectively.
- a tetrazole group is a heterocyclic group containing four nitrogen atoms in a five-membered ring.
- a triazole group and a tetrazole group are weakly basic as compared with other nitrogen-containing heterocyclic groups such as an imidazole group. It is advantageous from the viewpoint of improving storage stability.
- the compound (C) is preferably a compound having the above reactive group at the molecular end.
- the reactivity between the compound (C) and the resin (A) tends to be improved.
- the compound (C) preferably contains a compound represented by general formula (I).
- R 1 is a hydrogen atom or a methyl group
- R 2 is a hydrogen atom, a halogen atom, a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted cycloalkyl group having 3 to 15 carbon atoms, or 6 to 20 carbon atoms; is a substituted or unsubstituted aromatic hydrocarbon group
- X is -S- or -NH-
- A is —O—(CH2) m — or a single bond
- m is a positive integer from 1 to 10
- n is a positive integer from 1 to 10;
- X is preferably -S-.
- compound (C) examples include the following. Of course, compound (C) is not limited to these.
- the content of the compound (C) is, for example, 0.1 parts by mass or more, preferably 0.5 parts by mass or more, more preferably 1 part by mass or more, relative to 100 parts by mass of the resin (A).
- the content of the compound (C) is, for example, 30 parts by mass or less, preferably 20 parts by mass or less, more preferably 10 parts by mass or less with respect to 100 parts by mass of the resin (A).
- the content of the compound (C) is 30 parts by mass or less, the ratio of the resin (A) in the photosensitive resin composition is maintained, and the resin film formed from the photosensitive resin composition has sufficient strength. become.
- the photosensitive resin composition of the present embodiment can optionally contain additives other than the resin (A) and compound (C) described above.
- the photosensitive resin composition of this embodiment preferably contains a polyfunctional (meth)acrylic compound.
- a polyfunctional (meth)acrylic compound refers to a resin having two or more (meth)acryloyl groups. It is believed that the polyfunctional (meth)acrylic compound forms a network structure that "wraps" the skeleton of the resin (A) by polymerization. It is presumed that the formation of such a complexly entangled structure improves the performance of the resin film.
- a polyfunctional (meth)acrylic compound represented by the following general formula can be used as an example of the polyfunctional (meth)acrylic compound.
- R' is a hydrogen atom or a methyl group
- n is 0 to 3
- R is a hydrogen atom or a (meth)acryloyl group.
- polyfunctional (meth)acrylic compounds include the following. Of course, polyfunctional (meth)acrylic compounds are not limited to these.
- Aronix M-400, Aronix M-460, Aronix M-402, Aronix M-510, Aronix M-520 (manufactured by Toagosei Co., Ltd.), KAYARAD T-1420, KAYARAD DPHA, KAYARAD DPCA20, KAYARAD DPCA30, KAYARAD DPCA60, KAYARAD DPCA120 (manufactured by Nippon Kayaku Co., Ltd.), Viscoat #230, Viscoat #300, Viscoat #802, Viscoat #2500, Viscoat #1000, Viscoat #1080 (manufactured by Osaka Organic Chemical Industry Co., Ltd.), NK Ester A-BPE-10 , NK Ester A-GLY-9E, NK Ester A-9550, and NK Ester A-DPH (manufactured by Shin-Nakamura Chemical Co., Ltd.).
- the amount of the polyfunctional (meth)acrylate compound relative to 100 parts by mass of the resin (A) is preferably 1 to 150 parts by mass, more preferably 20 to 120 parts by mass, and even more preferably 50 to 100 parts by mass.
- the resin (A) and the polyfunctional (meth)acrylate form an “entangled structure” upon curing.
- the resin (A) and the polyfunctional (meth) acrylate compound are moderately entangled, and the amount of extra components not involved in entanglement is thought to decrease. . And it is considered that the performance is further improved.
- the photosensitive resin composition contains a polyfunctional (meth)acrylic compound
- it may contain only one polyfunctional (meth)acrylate compound, or may contain two or more polyfunctional (meth)acrylate compounds. In the latter case, it is preferable to use together polyfunctional (meth)acrylate compounds having different numbers of functional groups.
- polyfunctional (meth)acrylate compounds having different numbers of functional groups By using polyfunctional (meth)acrylate compounds having different numbers of functional groups together, it is believed that a more complicated "entangled structure" is formed and the properties of the cured film are further improved.
- the resin (A) and a polyfunctional (meth)acrylic compound are used together, a polymerization reaction of the polyfunctional (meth)acrylic compound can be employed as the curing mechanism. Since this polymerization reaction does not involve dehydration in principle, the combined use of the resin (A) and the polyfunctional (meth)acrylic compound is also advantageous in that shrinkage due to heating is small.
- the photosensitive resin composition of this embodiment preferably contains a photosensitive agent.
- the photosensitive agent is not particularly limited as long as it can generate active species by light and cure the photosensitive resin composition.
- the photosensitizer preferably contains a photoradical generator.
- Photoradical generators are particularly effective in polymerizing polyfunctional (meth)acrylate compounds.
- the photoradical generator that can be used is not particularly limited, and known ones can be used as appropriate.
- Biimidazole compounds 1,2-octanedione, 1-[4-(phenylthio)phenyl]-2-(O-benzoyloxime), ethanone, 1-[9-ethyl-6-(2-methylbenzoyl)- 9H-carbazol-3-yl]-,1-(O-acetyloxime) and other oxime ester compounds; bis( ⁇ 5-2,4-cyclopentadien-1-yl)-bis(2,6-difluoro-3 -(1H-pyrrol-1-yl)-phenyl) titanocene compounds such as titanium; benzoic acid ester compounds such as p-dimethylaminobenzoic acid and p-diethylaminobenzoic acid; acridine compounds such as 9-phenylacridine; etc. can be mentioned.
- oxime ester compounds can be preferably used.
- photosensitive agent When using a photosensitive agent, only one photosensitive agent may be used, or two or more photosensitive agents may be used.
- the content of the photosensitizer is, for example, 1 to 30 parts by weight, preferably 5 to 20 parts by weight, per 100 parts by weight of the polyfunctional (meth)acrylate compound.
- the photosensitive resin composition of this embodiment may contain a thermal radical initiator.
- a thermal radical initiator accelerates the polymerization reaction of the polyfunctional (meth)acrylic compound and improves the heat resistance of the cured film. and/or the chemical resistance (resistance to organic solvents and the like) of the cured film can be increased.
- the thermal radical initiator preferably contains an organic peroxide.
- Organic peroxides include octanoyl peroxide, lauroyl peroxide, stearoyl peroxide, 1,1,3,3-tetramethylbutylperoxy 2-ethylhexanoate, oxalic acid peroxide, 2,5-dimethyl- 2,5-di(2-ethylhexanoylperoxy)hexane, 1-cyclohexyl-1-methylethylperoxy 2-ethylhexanoate, t-hexylperoxy 2-ethylhexanoate, t-butylperoxy 2-ethylhexanoate, m-toluyl peroxide, benzoyl peroxide, benzoyl peroxide, methyl ethyl ketone peroxide, acetyl peroxide, t-butyl hydroperoxide, di-t-butyl per
- thermal radical initiator when a thermal radical initiator is used, only one thermal radical initiator may be used, or two or more thermal radical initiators may be used. When a thermal radical initiator is used, its amount is preferably 0.1 to 30 parts by weight, more preferably 1 to 20 parts by weight, based on 100 parts by weight of the polyfunctional (meth)acrylic compound.
- the photosensitive resin composition of this embodiment may contain an epoxy resin.
- the epoxy resin is believed to form a bond with the resin (A), and the bond thus formed can enhance the mechanical properties (tensile elongation, etc.) of the cured film.
- epoxy resins include the following. Of course, epoxy resins are not limited to these. Bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol E type epoxy resin, bisphenol S type epoxy resin, hydrogenated bisphenol A type epoxy resin, bisphenol M type epoxy resin (4,4'-(1,3-phenylene isopridien) bisphenol type epoxy resin), bisphenol P type epoxy resin (4,4'-(1,4-phenylenediisopridiene) bisphenol type epoxy resin), bisphenol Z type epoxy resin (4,4'-cyclohexane Bisphenol-type epoxy resins such as cydiene bisphenol-type epoxy resin) and tetramethylbisphenol F-type epoxy resin; Resins, novolac type epoxy resins such as novolak type epoxy resins having a condensed ring aromatic hydrocarbon structure; biphenyl type epoxy resins; xylylene type epoxy resins, aralkyl type epoxy resins such as biphenyl aralkyl type epoxy resins; naphthylene
- an epoxy resin When an epoxy resin is used as an additive, its amount is, for example, 0.5 to 100 parts by mass, preferably 1 to 50 parts by mass, more preferably 3 to 20 parts by mass, relative to 100 parts by mass of the resin (A). be.
- epoxy resin when used as an additive, only one epoxy resin may be used, or two or more epoxy resins may be used together.
- the photosensitive resin composition of this embodiment may contain a curing catalyst.
- a curing catalyst promotes the polymerization reaction of the epoxy resin, and can further improve, for example, the tensile elongation of the cured film.
- Curing catalysts include compounds known as curing catalysts for epoxy resins (often called curing accelerators). For example, diazabicycloalkenes such as 1,8-diazabicyclo[5,4,0]undecene-7 and derivatives thereof; amine compounds such as tributylamine and benzyldimethylamine; imidazole compounds such as 2-methylimidazole; triphenyl Organic phosphines such as phosphine and methyldiphenylphosphine; tetra-substituted phosphonium salts such as phosphonium/tetranaphthyloxyborate and tetraphenylphosphonium/4,4'-sulfonyldiphenolate; and triphenylphosphine obtained by adducting benzoquinone. Among them, organic phosphines are preferred.
- its amount is, for example, 1 to 80 parts by mass, preferably 5 to 50 parts by mass, and more preferably 5 to 30 parts by mass with respect to 100 parts by mass of the epoxy resin.
- the photosensitive resin composition of this embodiment may contain a silane coupling agent.
- silane coupling agent By using the silane coupling agent, the adhesion between the resin film formed from the photosensitive resin composition and the substrate can be further enhanced.
- Silane coupling agents include, for example, amino group-containing silane coupling agents, epoxy group-containing silane coupling agents, (meth)acryloyl group-containing silane coupling agents, mercapto group-containing silane coupling agents, and vinyl group-containing silane coupling agents.
- a silane coupling agent such as a ureido group-containing silane coupling agent, a sulfide group-containing silane coupling agent, and a silane coupling agent having a cyclic anhydride structure can be used.
- a silane coupling agent having a cyclic anhydride structure is preferably used.
- the cyclic anhydride structure is likely to react with the main chain, side chains and/or terminals of the polyimide, and for this reason a particularly good effect of improving adhesion can be obtained.
- silane coupling agent When a silane coupling agent is used, it may be used alone, or two or more silane coupling agents may be used in combination.
- the amount used is, for example, 0.1 to 20 parts by mass, preferably 0.3 to 15 parts by mass, more preferably 0.3 to 15 parts by mass, when the amount of resin (A) used is 100 parts by mass. 0.4 to 12 parts by mass, more preferably 0.5 to 10 parts by mass.
- the photosensitive resin composition of this embodiment may contain a surfactant.
- a surfactant further enhances the applicability of the photosensitive resin composition and the flatness of the resin film formed from the photosensitive resin composition.
- surfactants include fluorine-based surfactants, silicone-based surfactants, alkyl-based surfactants, and acrylic surfactants.
- the surfactant is preferably nonionic. The use of nonionic surfactants is preferable, for example, from the viewpoint of suppressing unintentional reactions with other components in the composition and enhancing the storage stability of the composition.
- the surfactant preferably contains a surfactant containing at least one of a fluorine atom and a silicon atom. This contributes to obtaining a uniform resin film (improvement of coatability), improvement of developability, and improvement of adhesive strength.
- a surfactant is preferably, for example, a nonionic surfactant containing at least one of a fluorine atom and a silicon atom. Examples of commercial products that can be used as surfactants include F-251, F-253, F-281, F-430, and F-477 of "Megafac (registered trademark)" series manufactured by DIC Corporation.
- fluorine-containing oligomer structure surfactants fluorine-containing nonionic surfactants such as Phthagent 250 and Phthagent 251 manufactured by Neos Co., Ltd., SILFOAM (registered trademark) series manufactured by Wacker Chemie ( Examples include silicone surfactants such as SD 100 TS, SD 670, SD 850, SD 860, SD 882).
- FC4430 and FC4432 manufactured by 3M are also preferable surfactants.
- a surfactant When a surfactant is used, it may be used alone, or two or more surfactants may be used in combination.
- the photosensitive resin composition of the present embodiment contains a surfactant
- its amount is, for example, 0.001 to 1 part by mass, preferably 0.005, when the content of the resin (A) is 100 parts by mass. ⁇ 0.5 parts by mass.
- the photosensitive resin composition of this embodiment may contain water.
- the presence of water facilitates the hydrolysis reaction of the silane coupling agent, and tends to further increase the adhesion between the substrate and the cured film.
- the amount is preferably 0.1 to 5 parts by weight, based on 100 parts by weight of the total solid content (non-volatile components) of the photosensitive resin composition. It is preferably 0.2 to 3 parts by mass, more preferably 0.5 to 2 parts by mass.
- the water content of the photosensitive resin composition can be quantified by the Karl Fischer method.
- the photosensitive resin composition of this embodiment preferably contains a solvent. This makes it possible to easily form a photosensitive resin film on a base material (particularly, a base material having steps) by a coating method.
- a solvent usually contains an organic solvent.
- the organic solvent is not particularly limited as long as it can dissolve or disperse each component described above and does not substantially chemically react with each component.
- organic solvents include acetone, methyl ethyl ketone, toluene, propylene glycol methyl ethyl ether, propylene glycol dimethyl ether, propylene glycol 1-monomethyl ether 2-acetate, diethylene glycol ethyl methyl ether, diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether acetate, benzyl Alcohol, propylene carbonate, ethylene glycol diacetate, propylene glycol diacetate, propylene glycol monomethyl ether acetate, dipropylene glycol methyl-n-propyl ether, butyl acetate, ⁇ -butyrolactone, methyl lactate, ethyl lactate, butyl lactate and the like. . These may be used singly or in combination.
- the photosensitive resin composition of the present embodiment contains a solvent
- the photosensitive resin composition of the present embodiment is usually in the form of varnish. Since the photosensitive resin composition of the present embodiment is in the form of varnish, it is possible to form a uniform film by coating. Moreover, it is preferable that the photosensitive resin composition of the present embodiment is in the form of a varnish and that at least the resin (A) is dissolved in a solvent.
- the concentration of the total solid content in the photosensitive resin composition is preferably 10 to 50% by mass, more preferably 20 It is used so as to be ⁇ 45% by mass. By setting it as this range, each component can fully be melt
- the photosensitive resin composition of the present embodiment may contain components other than those listed above, if necessary.
- examples of such components include antioxidants, fillers such as silica, sensitizers, film-forming agents, and the like.
- the resin film of the present embodiment is made of a cured product of the above photosensitive resin composition.
- the above photosensitive resin composition can be applied onto a base material of an electronic device and cured to form a resin film.
- the electronic device of this embodiment includes the resin film described above.
- the electronic device of this embodiment can be manufactured by the following manufacturing process.
- the manufacturing process of the electronic device of this embodiment includes: A film forming step of forming a photosensitive resin film on a substrate using the photosensitive resin composition described above; an exposure step of exposing the photosensitive resin film; a developing step of developing the exposed photosensitive resin film; including.
- the method for manufacturing an electronic device of the present embodiment includes a thermosetting step of heating and curing the exposed photosensitive resin film after the above-described developing step. Thereby, a cured film having good heat resistance can be obtained.
- the film forming step is usually performed by applying a photosensitive resin composition onto the substrate.
- the film forming step can be performed using a spin coater, bar coater, spray device, inkjet device, or the like.
- Appropriate heating is preferably performed for the purpose of drying the solvent in the coated photosensitive resin composition before the next exposure step.
- the heating at this time is performed, for example, at a temperature of 80 to 150° C. for 1 to 60 minutes.
- the thickness of the photosensitive resin film after drying varies depending on the structure of the final electronic device to be obtained.
- the amount of exposure in the exposure step is not particularly limited. 100 to 2000 mJ/cm 2 is preferred, and 200 to 1000 mJ/cm 2 is more preferred.
- the light source used for exposure is not particularly limited as long as it emits light of a wavelength (eg, g-line or i-line) with which the photosensitive agent in the photosensitive resin composition reacts.
- a high pressure mercury lamp is typically used.
- Post-exposure baking may be performed as necessary.
- the post-exposure baking temperature is not particularly limited. It is preferably 50 to 150°C, more preferably 50 to 130°C, still more preferably 55 to 120°C, and particularly preferably 60 to 110°C.
- the post-exposure bake time is preferably 1 to 30 minutes, more preferably 1 to 20 minutes, still more preferably 1 to 15 minutes.
- a photomask can be used in the exposure step. Thereby, a desired "pattern" can be formed using the photosensitive resin composition.
- the developer used in the development process examples include an organic developer and a water-soluble developer.
- the developer preferably contains an organic solvent. More specifically, the developer is preferably a developer containing an organic solvent as a main component (a developer in which 95% by mass or more of the component is an organic solvent). By developing with a developer containing an organic solvent, swelling of the pattern due to the developer can be suppressed more than in the case of developing with an alkaline developer (aqueous). That is, it is easy to obtain a finer pattern.
- ketone solvents such as cyclopentanone
- ester solvents such as propylene glycol monomethyl ether acetate (PGMEA) and butyl acetate
- ether solvents such as propylene glycol monomethyl ether, etc.
- an organic solvent developer containing only an organic solvent and containing only unavoidable impurities may be used as the developer.
- Impurities that are unavoidably contained include metal elements and moisture, but from the viewpoint of preventing contamination of electronic devices, it is better that the impurities that are unavoidably contained are as small as possible.
- the method of bringing the developer into contact with the photosensitive resin film is not particularly limited.
- a generally known dipping method, paddle method, spray method, or the like can be appropriately applied.
- the time for the development process is usually in the range of about 5 to 300 seconds, preferably about 10 to 120 seconds, and is appropriately adjusted based on the film thickness of the resin film, the shape of the pattern to be formed, and the like.
- the conditions for the heat curing process are not particularly limited, but for example, the heating temperature can be about 160 to 250° C. for about 30 to 240 minutes.
- Resin (A-1) had a weight average molecular weight (Mw) of 50,000 by GPC measurement.
- Resin (A) (A-1) Resin synthesized above (imide ring structure-containing polyimide resin) (A-2) Resin synthesized above (polyamide acid ester resin)
- Polyfunctional (meth) acrylic compound (D-1) Viscoat #802 (manufactured by Osaka Organic Industry Co., Ltd., polyfunctional acrylic compound) (D-2) A-9550 (manufactured by Shin-Nakamura Chemical Co., Ltd., polyfunctional acrylic compound) (D-3) Viscoat #300 (manufactured by Osaka Organic Industry Co., Ltd., polyfunctional acrylic compound) (D-4) Viscoat #230 (manufactured by Osaka Organic Industry Co., Ltd., polyfunctional acrylic compound)
- Photosensitive agent (E-1) Irugacure OXE02 (manufactured by BASF, oxime ester type photoradical generator)
- Curing catalyst (H-1) Curing catalyst synthesized above (phosphonium salt)
- J-2) KBM-503 manufactured by Shin-Etsu Chemical Co., Ltd.
- ⁇ Tape test> Using a cutter, 100 patterns of 1 mm ⁇ 1 mm were formed on the film on the substrate obtained in the preparation of the tape test substrate. Next, after affixing Cellotape (registered trademark) with a peel strength of 3.0 mN/10 mm to the surface of the pattern, Cellotape (registered trademark) was peeled off vertically. Then, the number of peeled patterns was counted. In this evaluation, it was evaluated that the adhesion to copper was better as the number of peeled patterns was smaller.
- Cellotape registered trademark
- the substrate obtained in the preparation of the 90-degree peel strength evaluation substrate is set in a 90-degree peel strength measuring device (manufactured by Shimadzu Corporation, AUTOGRAPH AG-Xplus), and 1 cm is peeled at a peeling speed of 20 mm / min. and evaluated the average value of the peel strength.
- the unit of 90 degree peel strength is N/cm. A higher 90-degree peel strength is preferable from the standpoint of reliability.
- test piece 50 mm ⁇ 5 mm ⁇ 10 ⁇ m thick.
- Tg glass transition temperature
- a test piece was prepared in the same manner as in ⁇ Measurement of glass transition temperature (Tg)>.
- the resulting test piece was subjected to a tensile test using a tensile tester (Tensilon RTC-1210A, manufactured by Orientec Co., Ltd.) in an atmosphere of 23° C. in accordance with JIS K 7161, and the tensile elongation of the test piece was measured. It was measured.
- the drawing speed in the tensile test was 5 mm/min.
- the unit of tensile elongation is %.
- the photosensitive resin composition was spin-coated on a 12-inch silicon wafer having a plated copper layer of 3000 ⁇ on the surface so that the film thickness after drying was 5 ⁇ m, and dried on a hot plate at 100° C. for 3 minutes. , to obtain a photosensitive resin film.
- This photosensitive resin film is passed through a Toppan Printing Co., Ltd. mask (test chart No. 1: a left pattern and a blank pattern with a width of 0.5 to 50 ⁇ m are drawn), an i-line stepper (NSR-4425i manufactured by Nikon Corporation). ) was used to irradiate the i-line while changing the exposure amount.
- the film was developed with cyclopentanone at 2500 rpm for 30 seconds, and then with propylene glycol monomethyl ether acetate at 2500 rpm for 10 seconds. Further, after air-drying by spin drying at 2500 rpm for 10 seconds, drying was performed on a hot plate at 120° C. for 2 minutes. After that, heat treatment was performed at 200° C. for 90 minutes in a nitrogen atmosphere to obtain a patterned cured film.
- the obtained pattern was observed, and the pattern with a via hole of 7 ⁇ m ⁇ was evaluated as ⁇ (very good), the pattern with a via hole with a diameter of 10 ⁇ m was evaluated as ⁇ (good), and the pattern with a via hole with a diameter of 10 ⁇ m was evaluated as ⁇ (bad). evaluated.
- Viscosity change rate [%] ⁇ (viscosity A - viscosity B) / viscosity A ⁇ x 100
- a Cu wiring substrate was prepared by forming comb-shaped Cu wiring having a width of 5 ⁇ m, a pitch of 5 ⁇ m, and a height of 5 ⁇ m on a 12-inch silicon wafer with an oxide film.
- the photosensitive resin composition is applied onto the Cu wiring substrate by spin coating so that the film thickness after drying (the thickness of the portion without wiring) is 10 ⁇ m, and dried at 120° C. for 3 minutes to make it photosensitive.
- a resin film was formed.
- the resulting photosensitive resin film was exposed to light at 300 mJ/cm 2 using an i-line stepper without passing through a photomask.
- the test sample obtained in the preparation of the thermal cycle test sample is set in a temperature cycle test device (TCT device) (manufactured by Espec, TSA-72EH-W), and the temperature is raised from -60 ° C. to 200 ° C. and then The treatment was performed for 200 cycles, one cycle being a temperature drop to -60°C. Subsequently, a cross section of the Cu wiring portion was taken out by FIB (focused ion beam) processing and observed by SEM. In each example and comparative example, a total of 10 interfaces between the wiring and the resin film were observed. When peeling was not observed at all 10 locations, it was evaluated as ⁇ (good), and when peeling was observed at even one location, it was evaluated as x (bad).
- TCT device temperature cycle test device
- FIB focused ion beam
- the photosensitive resin compositions of Examples 1 to 7 were superior to Comparative Example 1 in all of the tape test, 90° peel strength, and thermal cycle test results. From these evaluation results, it is understood that the photosensitive resin compositions of Examples 1 to 7 are excellent in adhesion to substrates.
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Abstract
The photosensitive resin composition characteristically comprises (A) at least one resin selected from the group consisting of polyimide resins and their precursors, polybenzoxazole resins and their precursors, polyamide resins, novolac resins, and cycloolefin resins, and (C) a compound having a five-membered nitrogenous heterocyclic group and at least one reactive group selected from the group consisting of the epoxy group and (meth)acryloyl group.
Description
本発明は、感光性樹脂組成物、樹脂膜および電子装置に関する。
The present invention relates to a photosensitive resin composition, a resin film and an electronic device.
電気・電子分野においては、絶縁層などの硬化膜を形成するために、ポリアミド樹脂および/またはポリイミド樹脂を含む感光性樹脂組成物が用いられることがある。そのため、ポリアミド樹脂および/またはポリイミド樹脂を含む感光性樹脂組成物がこれまで検討されてきている。
In the electrical and electronic fields, photosensitive resin compositions containing polyamide resins and/or polyimide resins are sometimes used to form cured films such as insulating layers. Therefore, photosensitive resin compositions containing polyamide resins and/or polyimide resins have been investigated.
一例として、特許文献1には、約20,000ダルトン~約70,000ダルトンの範囲の重量平均分子量を有する少なくとも1種の完全イミド化ポリイミドポリマー;少なくとも1種の溶解度スイッチング化合物;少なくとも1種の光開始剤;および少なくとも1種の溶剤を含み、シクロペンタノンを現像剤として使用した場合に約0.15μm/秒を超える溶解速度を示すフィルムを形成することができる感光性組成物が記載されている。
By way of example, US Pat. No. 5,300,002 discloses at least one fully imidized polyimide polymer having a weight average molecular weight ranging from about 20,000 Daltons to about 70,000 Daltons; at least one solubility-switching compound; at least one A photosensitive composition is described which comprises a photoinitiator; and at least one solvent and is capable of forming a film exhibiting a dissolution rate of greater than about 0.15 μm/sec when cyclopentanone is used as a developer. ing.
特許文献2、3、4などにも、ポリアミド樹脂および/またはポリイミド樹脂を含む感光性樹脂組成物が記載されている。
Patent Documents 2, 3, 4, etc. also describe photosensitive resin compositions containing polyamide resins and/or polyimide resins.
感光性樹脂組成物を用いて電子デバイス中に硬化膜を形成する場合、まず、感光性樹脂組成物を基材上に塗布して膜を形成し、その膜を露光や現像によりパターニングする。そして、そのパターニングされた膜を熱処理することで、硬化膜を形成する。
上記のような硬化膜の形成においては、感光性樹脂組成物と基材との密着性が高いことが好ましい。特に、近年では段差を有する基材上に平坦な硬化膜を形成することが求められているため、感光性樹脂組成物と基材との密着性向上がより一層求められる。 When forming a cured film in an electronic device using a photosensitive resin composition, first, the photosensitive resin composition is applied onto a substrate to form a film, and the film is patterned by exposure and development. Then, a cured film is formed by heat-treating the patterned film.
In the formation of the cured film as described above, it is preferable that the adhesion between the photosensitive resin composition and the substrate is high. In particular, in recent years, there has been a demand for forming a flat cured film on a base material having steps, so there is a further demand for improved adhesion between the photosensitive resin composition and the base material.
上記のような硬化膜の形成においては、感光性樹脂組成物と基材との密着性が高いことが好ましい。特に、近年では段差を有する基材上に平坦な硬化膜を形成することが求められているため、感光性樹脂組成物と基材との密着性向上がより一層求められる。 When forming a cured film in an electronic device using a photosensitive resin composition, first, the photosensitive resin composition is applied onto a substrate to form a film, and the film is patterned by exposure and development. Then, a cured film is formed by heat-treating the patterned film.
In the formation of the cured film as described above, it is preferable that the adhesion between the photosensitive resin composition and the substrate is high. In particular, in recent years, there has been a demand for forming a flat cured film on a base material having steps, so there is a further demand for improved adhesion between the photosensitive resin composition and the base material.
本発明はこのような事情に鑑みてなされたものである。本発明は、基材との密着が良好な感光性樹脂組成物を提供することを目的とする。
The present invention was made in view of such circumstances. An object of the present invention is to provide a photosensitive resin composition having good adhesion to a substrate.
本発明者らは、以下に提供される発明を完成させ、上記課題を解決した。
The inventors have completed the invention provided below and solved the above problems.
本発明によれば、
ポリイミド樹脂およびその前駆体、ポリベンゾオキサゾール樹脂およびその前駆体、ポリアミド樹脂、ノボラック樹脂、ならびにシクロオレフィン樹脂からなる群より選択される少なくとも一種以上の樹脂(A)と、
エポキシ基および(メタ)アクリロイル基からなる群より選択される少なくとも一種以上の反応性基、および5員環の含窒素複素環基を有する化合物(C)と、
を含有することを特徴とする感光性樹脂組成物
が提供される。 According to the invention,
At least one or more resins (A) selected from the group consisting of polyimide resins and their precursors, polybenzoxazole resins and their precursors, polyamide resins, novolak resins, and cycloolefin resins;
a compound (C) having at least one reactive group selected from the group consisting of an epoxy group and a (meth)acryloyl group, and a 5-membered nitrogen-containing heterocyclic group;
Provided is a photosensitive resin composition comprising:
ポリイミド樹脂およびその前駆体、ポリベンゾオキサゾール樹脂およびその前駆体、ポリアミド樹脂、ノボラック樹脂、ならびにシクロオレフィン樹脂からなる群より選択される少なくとも一種以上の樹脂(A)と、
エポキシ基および(メタ)アクリロイル基からなる群より選択される少なくとも一種以上の反応性基、および5員環の含窒素複素環基を有する化合物(C)と、
を含有することを特徴とする感光性樹脂組成物
が提供される。 According to the invention,
At least one or more resins (A) selected from the group consisting of polyimide resins and their precursors, polybenzoxazole resins and their precursors, polyamide resins, novolak resins, and cycloolefin resins;
a compound (C) having at least one reactive group selected from the group consisting of an epoxy group and a (meth)acryloyl group, and a 5-membered nitrogen-containing heterocyclic group;
Provided is a photosensitive resin composition comprising:
また、本発明によれば、
上記の感光性樹脂組成物の硬化物からなる樹脂膜
が提供される。 Moreover, according to the present invention,
A resin film comprising a cured product of the above photosensitive resin composition is provided.
上記の感光性樹脂組成物の硬化物からなる樹脂膜
が提供される。 Moreover, according to the present invention,
A resin film comprising a cured product of the above photosensitive resin composition is provided.
また、本発明によれば、
上記の樹脂膜を備える電子装置
が提供される。 Moreover, according to the present invention,
An electronic device comprising the above resin film is provided.
上記の樹脂膜を備える電子装置
が提供される。 Moreover, according to the present invention,
An electronic device comprising the above resin film is provided.
本発明によれば、基材との密着性が良好な感光性樹脂組成物が提供される。
According to the present invention, a photosensitive resin composition having good adhesion to a substrate is provided.
本明細書中、数値範囲の説明における「X~Y」との表記は、特に断らない限り、X以上Y以下のことを表す。例えば、「1~5質量%」とは「1質量%以上5質量%以下」を意味する。
本明細書における基(原子団)の表記において、置換か無置換かを記していない表記は、置換基を有しないものと置換基を有するものの両方を包含するものである。例えば「アルキル基」とは、置換基を有しないアルキル基(無置換アルキル基)のみならず、置換基を有するアルキル基(置換アルキル基)をも包含するものである。
本明細書における「(メタ)アクリル」との表記は、アクリルとメタクリルの両方を包含する概念を表す。「(メタ)アクリレート」等の類似の表記についても同様である。
本明細書における「有機基」の語は、特に断りが無い限り、有機化合物から1つ以上の水素原子を除いた原子団のことを意味する。例えば、「1価の有機基」とは、任意の有機化合物から1つの水素原子を除いた原子団のことを表す。
本明細書における「電子装置」の語は、半導体チップ、半導体素子、プリント配線基板、電気回路ディスプレイ装置、情報通信端末、発光ダイオード、物理電池、化学電池など、電子工学の技術が適用された素子、デバイス、最終製品等を包含する意味で用いられる。 In this specification, the notation "X to Y" in the description of numerical ranges means X or more and Y or less, unless otherwise specified. For example, "1 to 5% by mass" means "1% by mass or more and 5% by mass or less".
In the description of a group (atomic group) in the present specification, a description without indicating whether it is substituted or unsubstituted includes both those having no substituent and those having a substituent. For example, the term “alkyl group” includes not only alkyl groups without substituents (unsubstituted alkyl groups) but also alkyl groups with substituents (substituted alkyl groups).
The notation "(meth)acryl" used herein represents a concept that includes both acryl and methacryl. The same applies to similar notations such as "(meth)acrylate".
The term "organic group" as used herein means an atomic group obtained by removing one or more hydrogen atoms from an organic compound, unless otherwise specified. For example, a "monovalent organic group" represents an atomic group obtained by removing one hydrogen atom from an arbitrary organic compound.
The term "electronic device" as used herein refers to elements to which electronic engineering technology is applied, such as semiconductor chips, semiconductor elements, printed wiring boards, electric circuit display devices, information communication terminals, light-emitting diodes, physical batteries, and chemical batteries. , devices, final products, etc.
本明細書における基(原子団)の表記において、置換か無置換かを記していない表記は、置換基を有しないものと置換基を有するものの両方を包含するものである。例えば「アルキル基」とは、置換基を有しないアルキル基(無置換アルキル基)のみならず、置換基を有するアルキル基(置換アルキル基)をも包含するものである。
本明細書における「(メタ)アクリル」との表記は、アクリルとメタクリルの両方を包含する概念を表す。「(メタ)アクリレート」等の類似の表記についても同様である。
本明細書における「有機基」の語は、特に断りが無い限り、有機化合物から1つ以上の水素原子を除いた原子団のことを意味する。例えば、「1価の有機基」とは、任意の有機化合物から1つの水素原子を除いた原子団のことを表す。
本明細書における「電子装置」の語は、半導体チップ、半導体素子、プリント配線基板、電気回路ディスプレイ装置、情報通信端末、発光ダイオード、物理電池、化学電池など、電子工学の技術が適用された素子、デバイス、最終製品等を包含する意味で用いられる。 In this specification, the notation "X to Y" in the description of numerical ranges means X or more and Y or less, unless otherwise specified. For example, "1 to 5% by mass" means "1% by mass or more and 5% by mass or less".
In the description of a group (atomic group) in the present specification, a description without indicating whether it is substituted or unsubstituted includes both those having no substituent and those having a substituent. For example, the term “alkyl group” includes not only alkyl groups without substituents (unsubstituted alkyl groups) but also alkyl groups with substituents (substituted alkyl groups).
The notation "(meth)acryl" used herein represents a concept that includes both acryl and methacryl. The same applies to similar notations such as "(meth)acrylate".
The term "organic group" as used herein means an atomic group obtained by removing one or more hydrogen atoms from an organic compound, unless otherwise specified. For example, a "monovalent organic group" represents an atomic group obtained by removing one hydrogen atom from an arbitrary organic compound.
The term "electronic device" as used herein refers to elements to which electronic engineering technology is applied, such as semiconductor chips, semiconductor elements, printed wiring boards, electric circuit display devices, information communication terminals, light-emitting diodes, physical batteries, and chemical batteries. , devices, final products, etc.
[感光性樹脂組成物]
本実施形態の感光性樹脂組成物は、ポリイミド樹脂およびその前駆体、ポリベンゾオキサゾール樹脂およびその前駆体、ポリアミド樹脂、ノボラック樹脂、ならびにシクロオレフィン樹脂からなる群より選択される少なくとも一種以上の樹脂(A)と、エポキシ基および(メタ)アクリロイル基からなる群より選択される少なくとも一種以上の反応性基、および5員環の含窒素複素環基を有する化合物(C)と、を含有する。 [Photosensitive resin composition]
The photosensitive resin composition of the present embodiment includes at least one or more resins selected from the group consisting of polyimide resins and their precursors, polybenzoxazole resins and their precursors, polyamide resins, novolak resins, and cycloolefin resins ( A) and a compound (C) having at least one or more reactive groups selected from the group consisting of epoxy groups and (meth)acryloyl groups and a 5-membered nitrogen-containing heterocyclic group.
本実施形態の感光性樹脂組成物は、ポリイミド樹脂およびその前駆体、ポリベンゾオキサゾール樹脂およびその前駆体、ポリアミド樹脂、ノボラック樹脂、ならびにシクロオレフィン樹脂からなる群より選択される少なくとも一種以上の樹脂(A)と、エポキシ基および(メタ)アクリロイル基からなる群より選択される少なくとも一種以上の反応性基、および5員環の含窒素複素環基を有する化合物(C)と、を含有する。 [Photosensitive resin composition]
The photosensitive resin composition of the present embodiment includes at least one or more resins selected from the group consisting of polyimide resins and their precursors, polybenzoxazole resins and their precursors, polyamide resins, novolak resins, and cycloolefin resins ( A) and a compound (C) having at least one or more reactive groups selected from the group consisting of epoxy groups and (meth)acryloyl groups and a 5-membered nitrogen-containing heterocyclic group.
電子デバイス中の硬化膜には、基材との密着性が求められる。本実施形態の感光性樹脂組成物から形成される硬化膜は、金属製の基材との密着性が良好である。
詳細は不明であるが、化合物(C)が有する含窒素複素環と基材表面との相互作用が、硬化膜と基材との密着性が向上に寄与するものと考えられる。さらに、化合物(C)が、エポキシ基および(メタ)アクリロイル基から選択される反応性基を有することで、化合物(C)と樹脂組成物に含まれる他の成分が反応したり、化合物(C)どうしで重合したりするようになり、化合物(C)が樹脂組成物と密接に絡み合うようになる。このことが硬化膜と基材との密着性をより一層向上させるものと考えられる。 A cured film in an electronic device is required to have adhesion to a substrate. A cured film formed from the photosensitive resin composition of the present embodiment has good adhesion to a metal substrate.
Although the details are unknown, it is believed that the interaction between the nitrogen-containing heterocycle of the compound (C) and the substrate surface contributes to the improvement of the adhesion between the cured film and the substrate. Furthermore, since the compound (C) has a reactive group selected from an epoxy group and a (meth)acryloyl group, the compound (C) reacts with other components contained in the resin composition, or the compound (C ), and the compound (C) becomes closely entangled with the resin composition. It is believed that this further improves the adhesion between the cured film and the substrate.
詳細は不明であるが、化合物(C)が有する含窒素複素環と基材表面との相互作用が、硬化膜と基材との密着性が向上に寄与するものと考えられる。さらに、化合物(C)が、エポキシ基および(メタ)アクリロイル基から選択される反応性基を有することで、化合物(C)と樹脂組成物に含まれる他の成分が反応したり、化合物(C)どうしで重合したりするようになり、化合物(C)が樹脂組成物と密接に絡み合うようになる。このことが硬化膜と基材との密着性をより一層向上させるものと考えられる。 A cured film in an electronic device is required to have adhesion to a substrate. A cured film formed from the photosensitive resin composition of the present embodiment has good adhesion to a metal substrate.
Although the details are unknown, it is believed that the interaction between the nitrogen-containing heterocycle of the compound (C) and the substrate surface contributes to the improvement of the adhesion between the cured film and the substrate. Furthermore, since the compound (C) has a reactive group selected from an epoxy group and a (meth)acryloyl group, the compound (C) reacts with other components contained in the resin composition, or the compound (C ), and the compound (C) becomes closely entangled with the resin composition. It is believed that this further improves the adhesion between the cured film and the substrate.
上記のような事項から、本実施形態の感光性樹脂組成物は、電子装置における絶縁層の形成に好ましく用いられる。
From the above matters, the photosensitive resin composition of the present embodiment is preferably used for forming insulating layers in electronic devices.
本実施形態の感光性樹脂組成物が含むことができる成分や、本実施形態の感光性樹脂組成物の性状、物性などについて説明を続ける。
The description of the components that the photosensitive resin composition of the present embodiment can contain and the properties and physical properties of the photosensitive resin composition of the present embodiment will be continued.
<樹脂(A)>
本実施形態の感光性樹脂組成物は、ポリイミド樹脂およびその前駆体、ポリベンゾオキサゾール樹脂およびその前駆体、ポリアミド樹脂、ノボラック樹脂、ならびにシクロオレフィン樹脂から成る群より選択される1種以上の樹脂(A)を含有する。 <Resin (A)>
The photosensitive resin composition of the present embodiment includes one or more resins selected from the group consisting of polyimide resins and their precursors, polybenzoxazole resins and their precursors, polyamide resins, novolac resins, and cycloolefin resins ( A).
本実施形態の感光性樹脂組成物は、ポリイミド樹脂およびその前駆体、ポリベンゾオキサゾール樹脂およびその前駆体、ポリアミド樹脂、ノボラック樹脂、ならびにシクロオレフィン樹脂から成る群より選択される1種以上の樹脂(A)を含有する。 <Resin (A)>
The photosensitive resin composition of the present embodiment includes one or more resins selected from the group consisting of polyimide resins and their precursors, polybenzoxazole resins and their precursors, polyamide resins, novolac resins, and cycloolefin resins ( A).
本実施形態の感光性樹脂組成物は、樹脂(A)を1種のみ含んでもよいし、2種以上含んでもよい。
The photosensitive resin composition of the present embodiment may contain only one resin (A), or may contain two or more resins (A).
本実施形態の感光性樹脂組成物における樹脂(A)の含有量は、感光性樹脂組成物の全固形分中、好適には1質量%以上、より好適には5質量%以上、さらに好適には10質量%以上である。ある程度多量の樹脂(A)を用いることで、適度な厚さの樹脂膜を形成しやすくなる。また、樹脂(A)の上限値は特に限定されないが、通常は60質量%以下、好適には50質量%以下である。
The content of the resin (A) in the photosensitive resin composition of the present embodiment is preferably 1% by mass or more, more preferably 5% by mass or more, more preferably 5% by mass or more, based on the total solid content of the photosensitive resin composition. is 10% by mass or more. By using a large amount of resin (A) to some extent, it becomes easier to form a resin film having an appropriate thickness. The upper limit of resin (A) is not particularly limited, but is usually 60% by mass or less, preferably 50% by mass or less.
(ポリイミド樹脂)
加熱による収縮を抑えることができるという観点から、本実施形態の感光性樹脂組成物は、樹脂(A)としてポリイミド樹脂を含むことが好ましい。 (polyimide resin)
From the viewpoint of being able to suppress shrinkage due to heating, the photosensitive resin composition of the present embodiment preferably contains a polyimide resin as the resin (A).
加熱による収縮を抑えることができるという観点から、本実施形態の感光性樹脂組成物は、樹脂(A)としてポリイミド樹脂を含むことが好ましい。 (polyimide resin)
From the viewpoint of being able to suppress shrinkage due to heating, the photosensitive resin composition of the present embodiment preferably contains a polyimide resin as the resin (A).
ポリイミド樹脂を用いる場合、1のみのポリイミド樹脂を用いてもよいし、2以上のポリイミド樹脂を併用してもよい。
When using a polyimide resin, only one polyimide resin may be used, or two or more polyimide resins may be used together.
ポリイミド樹脂中に含まれるイミド環基のモル数をIMとし、ポリイミド樹脂に含まれるアミド基のモル数をAMとしたとき、{IM/(IM+AM)}×100(%)で表されるイミド環化率は、好ましくは90%以上、より好ましくは95%以上、さらに好ましくは98%以上である。要するに、ポリイミド樹脂は、アミド構造が無いまたは少なく、イミド環構造が多い樹脂であることが好ましい。このようなポリイミド樹脂を用いることで、閉環反応による脱水が起こらないため、加熱による収縮(硬化収縮)を一層抑えることができる。これにより、電子デバイスの信頼性の一層の向上や、硬化膜の平坦性の一層の向上などを図ることができる。
イミド環化率は、一例として、NMRスペクトルにおける、アミド基に対応するピークの面積やイミド環基に対応するピークの面積などから知ることができる。別の例として、イミド環化率は、赤外吸収スペクトルにおける、アミド基に対応するピークの面積やイミド環基に対応するピークの面積などから知ることができる。 When the number of moles of the imide ring group contained in the polyimide resin is IM and the number of moles of the amide group contained in the polyimide resin is AM, the imide ring represented by {IM/(IM+AM)}×100(%) The conversion rate is preferably 90% or higher, more preferably 95% or higher, and still more preferably 98% or higher. In short, the polyimide resin preferably has no or little amide structure and many imide ring structures. By using such a polyimide resin, dehydration due to a ring closure reaction does not occur, so shrinkage due to heating (curing shrinkage) can be further suppressed. This makes it possible to further improve the reliability of the electronic device and further improve the flatness of the cured film.
The imide cyclization rate can be known, for example, from the area of the peak corresponding to the amide group and the area of the peak corresponding to the imide ring group in the NMR spectrum. As another example, the imide cyclization rate can be known from the area of the peak corresponding to the amide group, the area of the peak corresponding to the imide ring group, and the like in the infrared absorption spectrum.
イミド環化率は、一例として、NMRスペクトルにおける、アミド基に対応するピークの面積やイミド環基に対応するピークの面積などから知ることができる。別の例として、イミド環化率は、赤外吸収スペクトルにおける、アミド基に対応するピークの面積やイミド環基に対応するピークの面積などから知ることができる。 When the number of moles of the imide ring group contained in the polyimide resin is IM and the number of moles of the amide group contained in the polyimide resin is AM, the imide ring represented by {IM/(IM+AM)}×100(%) The conversion rate is preferably 90% or higher, more preferably 95% or higher, and still more preferably 98% or higher. In short, the polyimide resin preferably has no or little amide structure and many imide ring structures. By using such a polyimide resin, dehydration due to a ring closure reaction does not occur, so shrinkage due to heating (curing shrinkage) can be further suppressed. This makes it possible to further improve the reliability of the electronic device and further improve the flatness of the cured film.
The imide cyclization rate can be known, for example, from the area of the peak corresponding to the amide group and the area of the peak corresponding to the imide ring group in the NMR spectrum. As another example, the imide cyclization rate can be known from the area of the peak corresponding to the amide group, the area of the peak corresponding to the imide ring group, and the like in the infrared absorption spectrum.
ポリイミド樹脂は、下記一般式(PI-1)で表される構造単位を含むことが好ましい。
The polyimide resin preferably contains a structural unit represented by the following general formula (PI-1).
一般式(PI-1)中、
Xは2価の有機基であり、
Yは4価の有機基であり、
XおよびYの少なくとも一方は、フッ素原子含有基である。 In general formula (PI-1),
X is a divalent organic group,
Y is a tetravalent organic group,
At least one of X and Y is a fluorine atom-containing group.
Xは2価の有機基であり、
Yは4価の有機基であり、
XおよびYの少なくとも一方は、フッ素原子含有基である。 In general formula (PI-1),
X is a divalent organic group,
Y is a tetravalent organic group,
At least one of X and Y is a fluorine atom-containing group.
Xの2価の有機基および/またはYの4価の有機基は、芳香環構造を含むことが好ましく、ベンゼン環構造を含むことがより好ましい。これにより耐熱性が一層高まる傾向がある。
有機溶剤溶解性の観点では、XおよびYの両方が、フッ素原子含有基であることが好ましい。
Xの2価の有機基および/またはYの4価の有機基は、好ましくは、2~6個のベンゼン環が、単結合または2価の連結基を介して結合した構造を有する。ここでの2価の連結基としては、アルキレン基、フッ化アルキレン基、エーテル基などを挙げることができる。アルキレン基およびフッ化アルキレン基は、直鎖状であっても分岐状であってもよい。
Xの2価の有機基の炭素数は、例えば6~30である。
Yの4価の有機基の炭素数は、例えば6~20である。
一般式(PI-1)中の2つのイミド環は、それぞれ、5員環であることが好ましい。 The divalent organic group of X and/or the tetravalent organic group of Y preferably contains an aromatic ring structure, more preferably a benzene ring structure. This tends to further increase the heat resistance.
From the viewpoint of solubility in organic solvents, both X and Y are preferably fluorine atom-containing groups.
The divalent organic group of X and/or the tetravalent organic group of Y preferably has a structure in which 2 to 6 benzene rings are linked via a single bond or a divalent linking group. Examples of the divalent linking group here include an alkylene group, a fluorinated alkylene group, an ether group, and the like. Alkylene groups and fluorinated alkylene groups may be linear or branched.
The number of carbon atoms in the divalent organic group of X is, for example, 6-30.
The number of carbon atoms in the tetravalent organic group of Y is, for example, 6-20.
Each of the two imide rings in general formula (PI-1) is preferably a 5-membered ring.
有機溶剤溶解性の観点では、XおよびYの両方が、フッ素原子含有基であることが好ましい。
Xの2価の有機基および/またはYの4価の有機基は、好ましくは、2~6個のベンゼン環が、単結合または2価の連結基を介して結合した構造を有する。ここでの2価の連結基としては、アルキレン基、フッ化アルキレン基、エーテル基などを挙げることができる。アルキレン基およびフッ化アルキレン基は、直鎖状であっても分岐状であってもよい。
Xの2価の有機基の炭素数は、例えば6~30である。
Yの4価の有機基の炭素数は、例えば6~20である。
一般式(PI-1)中の2つのイミド環は、それぞれ、5員環であることが好ましい。 The divalent organic group of X and/or the tetravalent organic group of Y preferably contains an aromatic ring structure, more preferably a benzene ring structure. This tends to further increase the heat resistance.
From the viewpoint of solubility in organic solvents, both X and Y are preferably fluorine atom-containing groups.
The divalent organic group of X and/or the tetravalent organic group of Y preferably has a structure in which 2 to 6 benzene rings are linked via a single bond or a divalent linking group. Examples of the divalent linking group here include an alkylene group, a fluorinated alkylene group, an ether group, and the like. Alkylene groups and fluorinated alkylene groups may be linear or branched.
The number of carbon atoms in the divalent organic group of X is, for example, 6-30.
The number of carbon atoms in the tetravalent organic group of Y is, for example, 6-20.
Each of the two imide rings in general formula (PI-1) is preferably a 5-membered ring.
ポリイミド樹脂は、下記一般式(PI-2)で表される構造単位を含むことがより好ましい。
The polyimide resin more preferably contains a structural unit represented by the following general formula (PI-2).
一般式(PI-2)中、
Xは、一般式(PI-1)におけるXと同義であり、
Y'は、単結合またはアルキレン基を表す。 In the general formula (PI-2),
X is synonymous with X in the general formula (PI-1),
Y' represents a single bond or an alkylene group.
Xは、一般式(PI-1)におけるXと同義であり、
Y'は、単結合またはアルキレン基を表す。 In the general formula (PI-2),
X is synonymous with X in the general formula (PI-1),
Y' represents a single bond or an alkylene group.
Xの具体的態様については、一般式(PI-1)において説明したものと同様である。
Y'のアルキレン基は、直鎖状でも分岐状でもよい。Y'のアルキレン基の水素原子の一部または全部は、フッ素原子で置換されていることが好ましい。Y'のアルキレン基の炭素数は、例えば1~6、好ましくは1~4、さらに好ましくは1~3である。 Specific aspects of X are the same as those described for general formula (PI-1).
The alkylene group of Y' may be linear or branched. Some or all of the hydrogen atoms in the alkylene group of Y' are preferably substituted with fluorine atoms. The number of carbon atoms in the alkylene group of Y' is, for example, 1-6, preferably 1-4, more preferably 1-3.
Y'のアルキレン基は、直鎖状でも分岐状でもよい。Y'のアルキレン基の水素原子の一部または全部は、フッ素原子で置換されていることが好ましい。Y'のアルキレン基の炭素数は、例えば1~6、好ましくは1~4、さらに好ましくは1~3である。 Specific aspects of X are the same as those described for general formula (PI-1).
The alkylene group of Y' may be linear or branched. Some or all of the hydrogen atoms in the alkylene group of Y' are preferably substituted with fluorine atoms. The number of carbon atoms in the alkylene group of Y' is, for example, 1-6, preferably 1-4, more preferably 1-3.
ポリイミド樹脂は、ポリイミド樹脂前駆体を閉環反応させることにより得ることができる。ポリイミド前駆体としては、ポリアミド樹脂を用いることができる。
A polyimide resin can be obtained by subjecting a polyimide resin precursor to a ring closure reaction. A polyamide resin can be used as the polyimide precursor.
ポリイミド樹脂および/またはポリイミド樹脂前駆体の重量平均分子量は、例えば5000~100000、好ましくは7000~75000、より好ましくは10000~50000である。ポリイミド樹脂および/またはポリイミド樹脂前駆体の重量平均分子量がある程度大きいことにより、例えば硬化膜の十分な耐熱性を得ることができる。また、ポリイミド樹脂および/またはポリイミド樹脂前駆体の重量平均分子量が大きすぎないことにより、ポリイミド樹脂および/またはポリイミド樹脂前駆体を有機溶剤に溶解させやすくなる。
重量平均分子量は、通常、ポリスチレンを標準物質として用いたゲルパーミエーションクロマトグラフィー(GPC)法により求めることができる。 The weight average molecular weight of the polyimide resin and/or polyimide resin precursor is, for example, 5,000 to 100,000, preferably 7,000 to 75,000, and more preferably 10,000 to 50,000. When the weight average molecular weight of the polyimide resin and/or the polyimide resin precursor is large to some extent, for example, sufficient heat resistance of the cured film can be obtained. Moreover, when the weight average molecular weight of the polyimide resin and/or the polyimide resin precursor is not too large, the polyimide resin and/or the polyimide resin precursor can be easily dissolved in the organic solvent.
The weight average molecular weight can usually be determined by gel permeation chromatography (GPC) using polystyrene as a standard substance.
重量平均分子量は、通常、ポリスチレンを標準物質として用いたゲルパーミエーションクロマトグラフィー(GPC)法により求めることができる。 The weight average molecular weight of the polyimide resin and/or polyimide resin precursor is, for example, 5,000 to 100,000, preferably 7,000 to 75,000, and more preferably 10,000 to 50,000. When the weight average molecular weight of the polyimide resin and/or the polyimide resin precursor is large to some extent, for example, sufficient heat resistance of the cured film can be obtained. Moreover, when the weight average molecular weight of the polyimide resin and/or the polyimide resin precursor is not too large, the polyimide resin and/or the polyimide resin precursor can be easily dissolved in the organic solvent.
The weight average molecular weight can usually be determined by gel permeation chromatography (GPC) using polystyrene as a standard substance.
(ポリベンゾオキサゾール樹脂)
ポリベンゾオキサゾール樹脂は、下記一般式(PB01)で表される構造単位を含むことが好ましい。 (polybenzoxazole resin)
The polybenzoxazole resin preferably contains a structural unit represented by the following general formula (PB01).
ポリベンゾオキサゾール樹脂は、下記一般式(PB01)で表される構造単位を含むことが好ましい。 (polybenzoxazole resin)
The polybenzoxazole resin preferably contains a structural unit represented by the following general formula (PB01).
ポリベンゾオキサゾール樹脂を用いる場合、1のみのベンゾオキサゾール樹脂を用いてもよいし、2以上のポリベンゾオキサゾール樹脂を併用してもよい。
When using a polybenzoxazole resin, only one benzoxazole resin may be used, or two or more polybenzoxazole resins may be used in combination.
ポリベンゾオキサゾール樹脂は、ポリベンゾオキサゾール樹脂前駆体を閉環反応させることにより得ることができる。ポリベンゾオキサゾール樹脂前駆体としては、ポリアミド樹脂を用いることができる。
A polybenzoxazole resin can be obtained by subjecting a polybenzoxazole resin precursor to a ring-closure reaction. A polyamide resin can be used as the polybenzoxazole resin precursor.
(ポリアミド樹脂)
ポリアミド樹脂は、下記一般式(PA-1)で表される構造単位を含むことが好ましい。 (polyamide resin)
The polyamide resin preferably contains a structural unit represented by general formula (PA-1) below.
ポリアミド樹脂は、下記一般式(PA-1)で表される構造単位を含むことが好ましい。 (polyamide resin)
The polyamide resin preferably contains a structural unit represented by general formula (PA-1) below.
ポリアミド樹脂を用いる場合、1のみのポリアミド樹脂を用いてもよいし、2以上のポリアミド樹脂を併用してもよい。
When a polyamide resin is used, only one polyamide resin may be used, or two or more polyamide resins may be used together.
一般式(PA-1)において、Xは2価の有機基であり、Yは4価の有機基であり、XおよびYの少なくとも一方は、好ましくは、フッ素原子含有基である。有機溶剤溶解性の観点では、一般式(PA-1)において、XおよびYの両方が、フッ素原子含有基であることが好ましい。
In general formula (PA-1), X is a divalent organic group, Y is a tetravalent organic group, and at least one of X and Y is preferably a fluorine atom-containing group. From the viewpoint of solubility in organic solvents, both X and Y in general formula (PA-1) are preferably fluorine atom-containing groups.
一般式(PA-1)において、Xの2価の有機基および/またはYの4価の有機基は、芳香環構造を含むことが好ましく、ベンゼン環構造を含むことがより好ましい。これにより耐熱性が一層高まる傾向がある。ここでのベンゼン環は、フッ素原子、フッ化アルキル基(好ましくはトリフルオロメチル基)などのフッ素原子含有基で置換されていてもよいし、その他の基で置換されていてもよい。
一般式(PA-1)におけるXの2価の有機基および/またはYの4価の有機基は、好ましくは、2~6個のベンゼン環が、単結合または2価の連結基を介して結合した構造を有する。ここでの2価の連結基としては、アルキレン基、フッ化アルキレン基、エーテル基などを挙げることができる。アルキレン基およびフッ化アルキレン基は、直鎖状であっても分岐状であってもよい。
一般式(PA-1)において、Xの2価の有機基の炭素数は、例えば6~30である。
一般式(PA-1)において、Yの4価の有機基の炭素数は、例えば6~20である。 In general formula (PA-1), the divalent organic group of X and/or the tetravalent organic group of Y preferably contains an aromatic ring structure, more preferably a benzene ring structure. This tends to further increase the heat resistance. The benzene ring here may be substituted with a fluorine atom-containing group such as a fluorine atom or a fluorinated alkyl group (preferably a trifluoromethyl group), or may be substituted with other groups.
The divalent organic group for X and/or the tetravalent organic group for Y in general formula (PA-1) preferably has 2 to 6 benzene rings via a single bond or a divalent linking group. It has a combined structure. Examples of the divalent linking group here include an alkylene group, a fluorinated alkylene group, an ether group, and the like. Alkylene groups and fluorinated alkylene groups may be linear or branched.
In general formula (PA-1), the number of carbon atoms in the divalent organic group of X is, for example, 6-30.
In general formula (PA-1), the tetravalent organic group of Y has, for example, 6 to 20 carbon atoms.
一般式(PA-1)におけるXの2価の有機基および/またはYの4価の有機基は、好ましくは、2~6個のベンゼン環が、単結合または2価の連結基を介して結合した構造を有する。ここでの2価の連結基としては、アルキレン基、フッ化アルキレン基、エーテル基などを挙げることができる。アルキレン基およびフッ化アルキレン基は、直鎖状であっても分岐状であってもよい。
一般式(PA-1)において、Xの2価の有機基の炭素数は、例えば6~30である。
一般式(PA-1)において、Yの4価の有機基の炭素数は、例えば6~20である。 In general formula (PA-1), the divalent organic group of X and/or the tetravalent organic group of Y preferably contains an aromatic ring structure, more preferably a benzene ring structure. This tends to further increase the heat resistance. The benzene ring here may be substituted with a fluorine atom-containing group such as a fluorine atom or a fluorinated alkyl group (preferably a trifluoromethyl group), or may be substituted with other groups.
The divalent organic group for X and/or the tetravalent organic group for Y in general formula (PA-1) preferably has 2 to 6 benzene rings via a single bond or a divalent linking group. It has a combined structure. Examples of the divalent linking group here include an alkylene group, a fluorinated alkylene group, an ether group, and the like. Alkylene groups and fluorinated alkylene groups may be linear or branched.
In general formula (PA-1), the number of carbon atoms in the divalent organic group of X is, for example, 6-30.
In general formula (PA-1), the tetravalent organic group of Y has, for example, 6 to 20 carbon atoms.
ポリアミド樹脂は、下記一般式(PA-2)で表される構造単位を含むことがより好ましい。
The polyamide resin more preferably contains a structural unit represented by the following general formula (PA-2).
一般式(PA-2)中、
Xは、一般式(PA-1)におけるXと同義であり、
Y'は、単結合またはアルキレン基を表す。 In general formula (PA-2),
X is synonymous with X in the general formula (PA-1),
Y' represents a single bond or an alkylene group.
Xは、一般式(PA-1)におけるXと同義であり、
Y'は、単結合またはアルキレン基を表す。 In general formula (PA-2),
X is synonymous with X in the general formula (PA-1),
Y' represents a single bond or an alkylene group.
前述の通り、ポリアミド樹脂は、ポリイミド樹脂前駆体またはポリベンゾオキサゾール樹脂前駆体として用いることも可能である。
As mentioned above, the polyamide resin can also be used as a polyimide resin precursor or a polybenzoxazole resin precursor.
(ノボラック樹脂)
ノボラック樹脂は、フェノール類とアルデヒド類とを、無触媒または酸性触媒等の存在下で反応させて得られる樹脂であれば、用途に合わせて適宜選択することができる。たとえば、ランダムノボラック型やハイオルソノボラック型のものも用いることができる。 (novolac resin)
The novolak resin can be appropriately selected according to the application as long as it is a resin obtained by reacting phenols and aldehydes in the absence of a catalyst or in the presence of an acidic catalyst or the like. For example, a random novolak type or a high ortho novolac type can be used.
ノボラック樹脂は、フェノール類とアルデヒド類とを、無触媒または酸性触媒等の存在下で反応させて得られる樹脂であれば、用途に合わせて適宜選択することができる。たとえば、ランダムノボラック型やハイオルソノボラック型のものも用いることができる。 (novolac resin)
The novolak resin can be appropriately selected according to the application as long as it is a resin obtained by reacting phenols and aldehydes in the absence of a catalyst or in the presence of an acidic catalyst or the like. For example, a random novolak type or a high ortho novolac type can be used.
ノボラック樹脂を用いる場合、1のみのノボラック樹脂を用いてもよいし、2以上のノボラック樹脂を併用してもよい。
When using a novolak resin, only one novolak resin may be used, or two or more novolak resins may be used in combination.
なお、このノボラック樹脂は、通常、フェノール類に対するアルデヒド類のモル比(アルデヒド類/フェノール類)を0.5~1.0に制御した上で、反応させて得ることができる。
The novolak resin can be obtained by reacting the aldehydes to the phenols at a molar ratio (aldehydes/phenols) of 0.5 to 1.0.
ノボラック樹脂を調製する際に用いられるフェノール類の具体例としては、たとえば、フェノール、o-クレゾール、m-クレゾール、p-クレゾール、キシレノール、アルキルフェノール類、カテコール、レゾルシン等が挙げられる。なお、これらのフェノール類は単独、あるいは2種以上を混合して使用してもよい。
Specific examples of phenols used in preparing novolak resins include phenol, o-cresol, m-cresol, p-cresol, xylenol, alkylphenols, catechol, and resorcinol. These phenols may be used singly or in combination of two or more.
また、ノボラック樹脂を調製する際に用いられるアルデヒド類としては、たとえば、ホルムアルデヒド、パラホルムアルデヒド、ベンズアルデヒド等のアルデヒド化合物、およびこれらのアルデヒド化合物の発生源となる物質、あるいはこれらのアルデヒド化合物の溶液等を用いることができる。なお、これらのアルデヒド類は単独、あるいは2種以上を混合して使用してもよい。
Aldehydes used in preparing the novolac resin include, for example, aldehyde compounds such as formaldehyde, paraformaldehyde, and benzaldehyde, substances that are sources of these aldehyde compounds, and solutions of these aldehyde compounds. can be used. These aldehydes may be used alone or in combination of two or more.
(シクロオレフィン樹脂)
シクロオレフィン樹脂としては、シクロオレフィン構造を有する樹脂全般を適宜用いることができる。 (Cycloolefin resin)
As the cycloolefin resin, general resins having a cycloolefin structure can be appropriately used.
シクロオレフィン樹脂としては、シクロオレフィン構造を有する樹脂全般を適宜用いることができる。 (Cycloolefin resin)
As the cycloolefin resin, general resins having a cycloolefin structure can be appropriately used.
シクロオレフィン樹脂を用いる場合、1のみのシクロオレフィン樹脂を用いてもよいし、2以上のシクロオレフィン樹脂を併用してもよい。
When using a cycloolefin resin, only one cycloolefin resin may be used, or two or more cycloolefin resins may be used in combination.
例えば、ノルボルネンおよびノルボルネン誘導体からなる群より選択される1種または2種以上を重合または共重合させた重合反応物または共重合反応物を用いることができる。
シクロオレフィン系樹脂は、好ましくは、以下に説明するシクロオレフィン構造を有するモノマーに由来する構造単位を含む。また、さらに好ましくは、以下に説明する環状酸無水物構造を有するモノマーに由来する構造単位を含む。 For example, one or more selected from the group consisting of norbornene and norbornene derivatives may be polymerized or copolymerized or copolymerized.
The cycloolefin-based resin preferably contains a structural unit derived from a monomer having a cycloolefin structure described below. More preferably, it contains a structural unit derived from a monomer having a cyclic acid anhydride structure described below.
シクロオレフィン系樹脂は、好ましくは、以下に説明するシクロオレフィン構造を有するモノマーに由来する構造単位を含む。また、さらに好ましくは、以下に説明する環状酸無水物構造を有するモノマーに由来する構造単位を含む。 For example, one or more selected from the group consisting of norbornene and norbornene derivatives may be polymerized or copolymerized or copolymerized.
The cycloolefin-based resin preferably contains a structural unit derived from a monomer having a cycloolefin structure described below. More preferably, it contains a structural unit derived from a monomer having a cyclic acid anhydride structure described below.
シクロオレフィン構造を有するモノマーに由来する構造単位としては、下記一般式(a1)で示される、ノルボルネン系モノマー由来の構造単位が、好ましく挙げられる。
一般式(a1)中、R6、R7、R8およびR9はそれぞれ独立して水素、ハロゲン原子、または炭素数1~30の有機基であり、nは0、1または2である。 Structural units derived from monomers having a cycloolefin structure are preferably structural units derived from norbornene-based monomers represented by the following general formula (a1).
In general formula (a1), R 6 , R 7 , R 8 and R 9 are each independently hydrogen, a halogen atom or an organic group having 1 to 30 carbon atoms, and n is 0, 1 or 2.
一般式(a1)中、R6、R7、R8およびR9はそれぞれ独立して水素、ハロゲン原子、または炭素数1~30の有機基であり、nは0、1または2である。 Structural units derived from monomers having a cycloolefin structure are preferably structural units derived from norbornene-based monomers represented by the following general formula (a1).
In general formula (a1), R 6 , R 7 , R 8 and R 9 are each independently hydrogen, a halogen atom or an organic group having 1 to 30 carbon atoms, and n is 0, 1 or 2.
一般式(a1)中のR6~R9は、例えば、それぞれ独立して、水素、ハロゲン原子、または炭素数1~30の有機基であることができる。
R6~R9は、好ましくは、それぞれ独立して水素、ハロゲン原子、または炭素数1~10の有機基であり、より好ましくは、それぞれ独立して水素、ハロゲン原子、または炭素数1~3の有機基であり、さらに好ましくは、それぞれ独立して水素、ハロゲン原子、または炭素数1の有機基である。
R6~R9を構成する有機基(例えば炭素数1~30の有機基)は、その構造中にO、N、S、PおよびSiから選択される1以上の原子を含んでいてもよい。また、R6~R9のうち、任意の2つが互いに結合して、アルキリデン基、単環又は多環構造を形成してもよい。 R 6 to R 9 in general formula (a1) can be, for example, each independently hydrogen, a halogen atom, or an organic group having 1 to 30 carbon atoms.
R 6 to R 9 are preferably each independently hydrogen, halogen atoms or organic groups having 1 to 10 carbon atoms, more preferably each independently hydrogen, halogen atoms or 1 to 3 carbon atoms and more preferably each independently a hydrogen atom, a halogen atom, or an organic group having 1 carbon atoms.
The organic group (for example, an organic group having 1 to 30 carbon atoms) constituting R 6 to R 9 may contain one or more atoms selected from O, N, S, P and Si in its structure. . Any two of R 6 to R 9 may combine with each other to form an alkylidene group or a monocyclic or polycyclic structure.
R6~R9は、好ましくは、それぞれ独立して水素、ハロゲン原子、または炭素数1~10の有機基であり、より好ましくは、それぞれ独立して水素、ハロゲン原子、または炭素数1~3の有機基であり、さらに好ましくは、それぞれ独立して水素、ハロゲン原子、または炭素数1の有機基である。
R6~R9を構成する有機基(例えば炭素数1~30の有機基)は、その構造中にO、N、S、PおよびSiから選択される1以上の原子を含んでいてもよい。また、R6~R9のうち、任意の2つが互いに結合して、アルキリデン基、単環又は多環構造を形成してもよい。 R 6 to R 9 in general formula (a1) can be, for example, each independently hydrogen, a halogen atom, or an organic group having 1 to 30 carbon atoms.
R 6 to R 9 are preferably each independently hydrogen, halogen atoms or organic groups having 1 to 10 carbon atoms, more preferably each independently hydrogen, halogen atoms or 1 to 3 carbon atoms and more preferably each independently a hydrogen atom, a halogen atom, or an organic group having 1 carbon atoms.
The organic group (for example, an organic group having 1 to 30 carbon atoms) constituting R 6 to R 9 may contain one or more atoms selected from O, N, S, P and Si in its structure. . Any two of R 6 to R 9 may combine with each other to form an alkylidene group or a monocyclic or polycyclic structure.
<化合物(C)>
本実施形態の感光性樹脂組成物は、エポキシ基および(メタ)アクリロイル基からなる群より選択される少なくとも一種以上の反応性基、および5員環の含窒素複素環基を有する化合物(C)を含有する。 <Compound (C)>
The photosensitive resin composition of the present embodiment is a compound (C) having at least one or more reactive groups selected from the group consisting of epoxy groups and (meth)acryloyl groups, and a 5-membered nitrogen-containing heterocyclic group. contains
本実施形態の感光性樹脂組成物は、エポキシ基および(メタ)アクリロイル基からなる群より選択される少なくとも一種以上の反応性基、および5員環の含窒素複素環基を有する化合物(C)を含有する。 <Compound (C)>
The photosensitive resin composition of the present embodiment is a compound (C) having at least one or more reactive groups selected from the group consisting of epoxy groups and (meth)acryloyl groups, and a 5-membered nitrogen-containing heterocyclic group. contains
本実施形態の感光性樹脂組成物は、化合物(C)を1種のみ含んでもよいし、2種以上含んでもよい。
The photosensitive resin composition of the present embodiment may contain only one type of compound (C), or may contain two or more types.
化合物(C)が、5員環の含窒素複素環基を有することにより、感光性樹脂組成物と基材との密着性が向上する傾向がある。詳細は不明であるが、化合物(C)が有する含窒素複素環と基材表面との相互作用が、硬化膜と基材との密着性向上に寄与するものと考えられる。
さらに、化合物(C)が、エポキシ基および(メタ)アクリロイル基から選択される反応性基を有することで、化合物(C)と樹脂組成物に含まれる他の成分が反応したり、化合物(C)どうしで重合したりするようになり、化合物(C)が樹脂組成物と密接に絡み合うようになる。このことが硬化膜と基材との密着性をより一層向上させるものと考えられる。 When the compound (C) has a 5-membered nitrogen-containing heterocyclic group, the adhesion between the photosensitive resin composition and the substrate tends to be improved. Although the details are unknown, it is believed that the interaction between the nitrogen-containing heterocycle of the compound (C) and the surface of the substrate contributes to the improvement of adhesion between the cured film and the substrate.
Furthermore, since the compound (C) has a reactive group selected from an epoxy group and a (meth)acryloyl group, the compound (C) reacts with other components contained in the resin composition, or the compound (C ), and the compound (C) becomes closely entangled with the resin composition. It is believed that this further improves the adhesion between the cured film and the substrate.
さらに、化合物(C)が、エポキシ基および(メタ)アクリロイル基から選択される反応性基を有することで、化合物(C)と樹脂組成物に含まれる他の成分が反応したり、化合物(C)どうしで重合したりするようになり、化合物(C)が樹脂組成物と密接に絡み合うようになる。このことが硬化膜と基材との密着性をより一層向上させるものと考えられる。 When the compound (C) has a 5-membered nitrogen-containing heterocyclic group, the adhesion between the photosensitive resin composition and the substrate tends to be improved. Although the details are unknown, it is believed that the interaction between the nitrogen-containing heterocycle of the compound (C) and the surface of the substrate contributes to the improvement of adhesion between the cured film and the substrate.
Furthermore, since the compound (C) has a reactive group selected from an epoxy group and a (meth)acryloyl group, the compound (C) reacts with other components contained in the resin composition, or the compound (C ), and the compound (C) becomes closely entangled with the resin composition. It is believed that this further improves the adhesion between the cured film and the substrate.
尚、化合物(C)が有する5員環の含窒素複素環基は、金属の中でも特に銅との親和性が高いため、本実施形態の感光性樹脂組成物は、銅めっきされた基材など、基材表面に銅が存在する基材との密着性が特に優れる傾向にある。
In addition, since the five-membered nitrogen-containing heterocyclic group of the compound (C) has a particularly high affinity with copper among metals, the photosensitive resin composition of the present embodiment can be , the adhesiveness to substrates having copper on the substrate surface tends to be particularly excellent.
化合物(C)は、5員環の含窒素複素環基として、トリアゾール基およびテトラゾール基からなる群より選択される少なくとも一種以上の基を有する化合物であることが好ましい。
The compound (C) is preferably a compound having at least one group selected from the group consisting of a triazole group and a tetrazole group as a five-membered nitrogen-containing heterocyclic group.
トリアゾール基は、5員環に3つの窒素原子を含む複素環基である。窒素原子の位置が異なる2種の異性体があり、それぞれ1,2,3-トリアゾール基、1,2,4-トリアゾール基と呼ばれる。また、テトラゾール基は、5員環に4つの窒素原子を含む複素環基である。
A triazole group is a heterocyclic group containing three nitrogen atoms in a five-membered ring. There are two isomers with different positions of nitrogen atoms, which are called 1,2,3-triazole group and 1,2,4-triazole group, respectively. A tetrazole group is a heterocyclic group containing four nitrogen atoms in a five-membered ring.
トリアゾール基およびテトラゾール基は、イミダゾール基等の他の含窒素複素環基と比較して塩基性が弱く、これらを5員環の含窒素複素環基として採用することは、感光性樹脂組成物の保存性向上の観点から有利である。
A triazole group and a tetrazole group are weakly basic as compared with other nitrogen-containing heterocyclic groups such as an imidazole group. It is advantageous from the viewpoint of improving storage stability.
化合物(C)は、分子末端に上記反応性基を有する化合物であることが好ましい。
The compound (C) is preferably a compound having the above reactive group at the molecular end.
分子末端に上記反応性基を有することにより、化合物(C)と樹脂(A)との反応性が向上する傾向がある。
By having the above-mentioned reactive group at the molecular end, the reactivity between the compound (C) and the resin (A) tends to be improved.
化合物(C)は、一般式(I)で表される化合物を含むことが好ましい。
The compound (C) preferably contains a compound represented by general formula (I).
一般式(I)において、
R1は、水素原子またはメチル基であり、
R2は、水素原子、ハロゲン原子、炭素原子数1~20である置換もしくは非置換のアルキル基、炭素原子数3~15である置換もしくは非置換のシクロアルキル基、または炭素原子数6~20である置換もしくは非置換の芳香族炭化水素基であり、
Xは、-S-または-NH-であり、
Yは、-CH=または-N=であり、
Aは、-O-(CH2)m-または単結合であり、mは1~10の正の整数であり、
nは1~10の正の整数である。 In general formula (I),
R 1 is a hydrogen atom or a methyl group,
R 2 is a hydrogen atom, a halogen atom, a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted cycloalkyl group having 3 to 15 carbon atoms, or 6 to 20 carbon atoms; is a substituted or unsubstituted aromatic hydrocarbon group,
X is -S- or -NH-,
Y is -CH= or -N=,
A is —O—(CH2) m — or a single bond, m is a positive integer from 1 to 10;
n is a positive integer from 1 to 10;
R1は、水素原子またはメチル基であり、
R2は、水素原子、ハロゲン原子、炭素原子数1~20である置換もしくは非置換のアルキル基、炭素原子数3~15である置換もしくは非置換のシクロアルキル基、または炭素原子数6~20である置換もしくは非置換の芳香族炭化水素基であり、
Xは、-S-または-NH-であり、
Yは、-CH=または-N=であり、
Aは、-O-(CH2)m-または単結合であり、mは1~10の正の整数であり、
nは1~10の正の整数である。 In general formula (I),
R 1 is a hydrogen atom or a methyl group,
R 2 is a hydrogen atom, a halogen atom, a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted cycloalkyl group having 3 to 15 carbon atoms, or 6 to 20 carbon atoms; is a substituted or unsubstituted aromatic hydrocarbon group,
X is -S- or -NH-,
Y is -CH= or -N=,
A is —O—(CH2) m — or a single bond, m is a positive integer from 1 to 10;
n is a positive integer from 1 to 10;
一般式(I)において、Xは、-S-であることが好ましい。
In general formula (I), X is preferably -S-.
一般式(I)において、Xが-NH-であると、感光性樹脂組成物の塩基性が増大し、感光性樹脂組成物の保存性に悪影響を与えるおそれがあるためである。
This is because, in general formula (I), if X is -NH-, the basicity of the photosensitive resin composition increases, which may adversely affect the storage stability of the photosensitive resin composition.
化合物(C)の具体例としては、以下を挙げることができる。もちろん化合物(C)はこれらのみに限定されない。
Specific examples of the compound (C) include the following. Of course, compound (C) is not limited to these.
化合物(C)の含有量は、樹脂(A)100質量部に対して、例えば0.1質量部以上であり、好ましくは0.5質量部以上、より好ましくは1質量部以上である。化合物(C)の含有量が0.1質量部以上であることにより、感光性樹脂組成物と基材との密着性が十分に向上する。
また、化合物(C)の含有量は、樹脂(A)100質量部に対して、例えば30質量部以下であり、好ましくは20質量部以下、より好ましくは10質量部以下である。化合物(C)の含有量が30質量部以下であることにより、感光性樹脂組成物における樹脂(A)の比率が維持され、感光性樹脂組成物から形成される樹脂膜が十分な強度を有するようになる。 The content of the compound (C) is, for example, 0.1 parts by mass or more, preferably 0.5 parts by mass or more, more preferably 1 part by mass or more, relative to 100 parts by mass of the resin (A). When the content of the compound (C) is 0.1 parts by mass or more, the adhesion between the photosensitive resin composition and the substrate is sufficiently improved.
The content of the compound (C) is, for example, 30 parts by mass or less, preferably 20 parts by mass or less, more preferably 10 parts by mass or less with respect to 100 parts by mass of the resin (A). When the content of the compound (C) is 30 parts by mass or less, the ratio of the resin (A) in the photosensitive resin composition is maintained, and the resin film formed from the photosensitive resin composition has sufficient strength. become.
また、化合物(C)の含有量は、樹脂(A)100質量部に対して、例えば30質量部以下であり、好ましくは20質量部以下、より好ましくは10質量部以下である。化合物(C)の含有量が30質量部以下であることにより、感光性樹脂組成物における樹脂(A)の比率が維持され、感光性樹脂組成物から形成される樹脂膜が十分な強度を有するようになる。 The content of the compound (C) is, for example, 0.1 parts by mass or more, preferably 0.5 parts by mass or more, more preferably 1 part by mass or more, relative to 100 parts by mass of the resin (A). When the content of the compound (C) is 0.1 parts by mass or more, the adhesion between the photosensitive resin composition and the substrate is sufficiently improved.
The content of the compound (C) is, for example, 30 parts by mass or less, preferably 20 parts by mass or less, more preferably 10 parts by mass or less with respect to 100 parts by mass of the resin (A). When the content of the compound (C) is 30 parts by mass or less, the ratio of the resin (A) in the photosensitive resin composition is maintained, and the resin film formed from the photosensitive resin composition has sufficient strength. become.
<その他の添加剤>
本実施形態の感光性樹脂組成物は、上述した樹脂(A)および化合物(C)以外の添加剤を任意で含有することができる。 <Other additives>
The photosensitive resin composition of the present embodiment can optionally contain additives other than the resin (A) and compound (C) described above.
本実施形態の感光性樹脂組成物は、上述した樹脂(A)および化合物(C)以外の添加剤を任意で含有することができる。 <Other additives>
The photosensitive resin composition of the present embodiment can optionally contain additives other than the resin (A) and compound (C) described above.
(多官能(メタ)アクリル化合物)
本実施形態の感光性樹脂組成物は、好ましくは多官能(メタ)アクリル化合物を含む。
多官能(メタ)アクリル化合物とは、(メタ)アクリロイル基の個数が2以上である樹脂のことを指す。多官能(メタ)アクリル化合物は、重合により、樹脂(A)の骨格を「包む」ようなネットワーク構造を形成するものと考えられる。このような複雑に絡み合った構造が形成されることにより、樹脂膜の性能が良化すると推測される。 (Polyfunctional (meth)acrylic compound)
The photosensitive resin composition of this embodiment preferably contains a polyfunctional (meth)acrylic compound.
A polyfunctional (meth)acrylic compound refers to a resin having two or more (meth)acryloyl groups. It is believed that the polyfunctional (meth)acrylic compound forms a network structure that "wraps" the skeleton of the resin (A) by polymerization. It is presumed that the formation of such a complexly entangled structure improves the performance of the resin film.
本実施形態の感光性樹脂組成物は、好ましくは多官能(メタ)アクリル化合物を含む。
多官能(メタ)アクリル化合物とは、(メタ)アクリロイル基の個数が2以上である樹脂のことを指す。多官能(メタ)アクリル化合物は、重合により、樹脂(A)の骨格を「包む」ようなネットワーク構造を形成するものと考えられる。このような複雑に絡み合った構造が形成されることにより、樹脂膜の性能が良化すると推測される。 (Polyfunctional (meth)acrylic compound)
The photosensitive resin composition of this embodiment preferably contains a polyfunctional (meth)acrylic compound.
A polyfunctional (meth)acrylic compound refers to a resin having two or more (meth)acryloyl groups. It is believed that the polyfunctional (meth)acrylic compound forms a network structure that "wraps" the skeleton of the resin (A) by polymerization. It is presumed that the formation of such a complexly entangled structure improves the performance of the resin film.
(メタ)アクリロイル基の個数に上限は特に無いが、原料入手の容易性などから、例えば11程度である。
Although there is no particular upper limit to the number of (meth)acryloyl groups, it is, for example, about 11, considering the ease of obtaining raw materials.
大まかな傾向として、(メタ)アクリロイル基の個数が多い場合、硬化膜の耐薬品性が高まる傾向がある。一方、(メタ)アクリロイル基の個数が少ない場合、硬化膜の引張り伸びなどの機械物性が良好となる傾向がある。
As a general trend, when the number of (meth)acryloyl groups is large, the chemical resistance of the cured film tends to increase. On the other hand, when the number of (meth)acryloyl groups is small, mechanical properties such as tensile elongation of the cured film tend to be good.
多官能(メタ)アクリル化合物としては、一例として、以下一般式で表される多官能(メタ)アクリル化合物を用いることができる。以下一般式において、R'は水素原子またはメチル基、nは0~3、Rは水素原子または(メタ)アクリロイル基である。
As an example of the polyfunctional (meth)acrylic compound, a polyfunctional (meth)acrylic compound represented by the following general formula can be used. In the general formulas below, R' is a hydrogen atom or a methyl group, n is 0 to 3, and R is a hydrogen atom or a (meth)acryloyl group.
多官能(メタ)アクリル化合物の具体例としては、以下を挙げることができる。もちろん、多官能(メタ)アクリル化合物はこれらのみに限定されない。
Specific examples of polyfunctional (meth)acrylic compounds include the following. Of course, polyfunctional (meth)acrylic compounds are not limited to these.
エチレングリコールジ(メタ)アクリレート、トリメチロールプロパントリ(メタ)アクリレート、ジトリメチロールプロパンテトラ(メタ)アクリレート、ペンタエリスリトールトリ(メタ)アクリレート、ペンタエリスリトールテトラ(メタ)アクリレート、ジペンタエリスリトールペンタ(メタ)アクリレート、ジペンタエリスリトールヘキサ(メタ)アクリレート等のポリオールポリアクリレート類、ビスフェノールAジグリシジルエーテルのジ(メタ)アクリレート、ヘキサンジオールジグリシジルエーテルのジ(メタ)アクリレート等のエポキシアクリレート類、ポリイソシナネートとヒドロキシエチル(メタ)アクリレート等の水酸基含有(メタ)アクリレートの反応によって得られるウレタン(メタ)アクリレートなど。
Ethylene glycol di(meth)acrylate, trimethylolpropane tri(meth)acrylate, ditrimethylolpropane tetra(meth)acrylate, pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, dipentaerythritol penta(meth)acrylate , Polyol polyacrylates such as dipentaerythritol hexa (meth) acrylate, di (meth) acrylate of bisphenol A diglycidyl ether, epoxy acrylates such as di (meth) acrylate of hexanediol diglycidyl ether, polyisocyanate and urethane (meth)acrylates obtained by reaction of hydroxyl group-containing (meth)acrylates such as hydroxyethyl (meth)acrylate;
アロニックスM-400、アロニックスM-460、アロニックスM-402、アロニックスM-510、アロニックスM-520(東亜合成株式会社製)、KAYARAD T-1420、KAYARAD DPHA、KAYARAD DPCA20、KAYARAD DPCA30、KAYARAD DPCA60、KAYARAD DPCA120(日本化薬株式会社製)、ビスコート#230、ビスコート#300、ビスコート#802、ビスコート#2500、ビスコート#1000、ビスコート#1080(大阪有機化学工業株式会社製)、NKエステルA-BPE-10、NKエステルA-GLY-9E、NKエステルA-9550、NKエステルA-DPH(新中村化学工業株式会社製)などの市販品。
Aronix M-400, Aronix M-460, Aronix M-402, Aronix M-510, Aronix M-520 (manufactured by Toagosei Co., Ltd.), KAYARAD T-1420, KAYARAD DPHA, KAYARAD DPCA20, KAYARAD DPCA30, KAYARAD DPCA60, KAYARAD DPCA120 (manufactured by Nippon Kayaku Co., Ltd.), Viscoat #230, Viscoat #300, Viscoat #802, Viscoat #2500, Viscoat #1000, Viscoat #1080 (manufactured by Osaka Organic Chemical Industry Co., Ltd.), NK Ester A-BPE-10 , NK Ester A-GLY-9E, NK Ester A-9550, and NK Ester A-DPH (manufactured by Shin-Nakamura Chemical Co., Ltd.).
多官能(メタ)アクリレート化合物を用いる場合、樹脂(A)100質量部に対する多官能(メタ)アクリレート化合物の量は、好ましくは1~150質量部、より好ましくは20~120質量部、さらに好ましくは50~100質量部である。
When using a polyfunctional (meth)acrylate compound, the amount of the polyfunctional (meth)acrylate compound relative to 100 parts by mass of the resin (A) is preferably 1 to 150 parts by mass, more preferably 20 to 120 parts by mass, and even more preferably 50 to 100 parts by mass.
前述のように、本実施形態の感光性樹脂組成物においては、硬化により、樹脂(A)と多官能(メタ)アクリレートとの「絡み合い構造」が形成されると考えられるが、樹脂(A)に対する多官能(メタ)アクリレート化合物の使用量を適切に調整することで、樹脂(A)と多官能(メタ)アクリレート化合物が適度に絡み合い、また、絡み合いに関与しない余分な成分が少なくなると考えられる。そして、性能が一層良化すると考えられる。
As described above, in the photosensitive resin composition of the present embodiment, it is considered that the resin (A) and the polyfunctional (meth)acrylate form an “entangled structure” upon curing. By appropriately adjusting the amount of the polyfunctional (meth) acrylate compound used, the resin (A) and the polyfunctional (meth) acrylate compound are moderately entangled, and the amount of extra components not involved in entanglement is thought to decrease. . And it is considered that the performance is further improved.
感光性樹脂組成物が多官能(メタ)アクリル化合物を含む場合、1のみの多官能(メタ)アクリレート化合物を含んでもよいし、2以上の多官能(メタ)アクリレート化合物を含んでもよい。後者の場合、官能基数が異なる多官能(メタ)アクリレート化合物を併用することが好ましい。官能基数が異なる多官能(メタ)アクリレート化合物を併用することで、より複雑な「絡み合い構造」ができ、硬化膜の特性が一層向上すると考えられる。
ちなみに、市販の多官能(メタ)アクリレート化合物の中には、官能基数が異なる多官能(メタ)アクリレート化合物の混合物もある。 When the photosensitive resin composition contains a polyfunctional (meth)acrylic compound, it may contain only one polyfunctional (meth)acrylate compound, or may contain two or more polyfunctional (meth)acrylate compounds. In the latter case, it is preferable to use together polyfunctional (meth)acrylate compounds having different numbers of functional groups. By using polyfunctional (meth)acrylate compounds having different numbers of functional groups together, it is believed that a more complicated "entangled structure" is formed and the properties of the cured film are further improved.
Incidentally, among commercially available polyfunctional (meth)acrylate compounds, there is also a mixture of polyfunctional (meth)acrylate compounds having different numbers of functional groups.
ちなみに、市販の多官能(メタ)アクリレート化合物の中には、官能基数が異なる多官能(メタ)アクリレート化合物の混合物もある。 When the photosensitive resin composition contains a polyfunctional (meth)acrylic compound, it may contain only one polyfunctional (meth)acrylate compound, or may contain two or more polyfunctional (meth)acrylate compounds. In the latter case, it is preferable to use together polyfunctional (meth)acrylate compounds having different numbers of functional groups. By using polyfunctional (meth)acrylate compounds having different numbers of functional groups together, it is believed that a more complicated "entangled structure" is formed and the properties of the cured film are further improved.
Incidentally, among commercially available polyfunctional (meth)acrylate compounds, there is also a mixture of polyfunctional (meth)acrylate compounds having different numbers of functional groups.
また、樹脂(A)と多官能(メタ)アクリル化合物とを併用する場合、硬化のメカニズムとして、多官能(メタ)アクリル化合物の重合反応を採用することができる。この重合反応は、原理的に脱水を伴わないので、加熱による収縮が小さいという点でも、樹脂(A)と多官能(メタ)アクリル化合物との併用は有利である。
Also, when the resin (A) and a polyfunctional (meth)acrylic compound are used together, a polymerization reaction of the polyfunctional (meth)acrylic compound can be employed as the curing mechanism. Since this polymerization reaction does not involve dehydration in principle, the combined use of the resin (A) and the polyfunctional (meth)acrylic compound is also advantageous in that shrinkage due to heating is small.
(感光剤)
本実施形態の感光性樹脂組成物は、好ましくは感光剤を含む。
感光剤は、光により活性種を発生して感光性樹脂組成物を硬化させることが可能なものである限り、特に限定されない。 (Photosensitizer)
The photosensitive resin composition of this embodiment preferably contains a photosensitive agent.
The photosensitive agent is not particularly limited as long as it can generate active species by light and cure the photosensitive resin composition.
本実施形態の感光性樹脂組成物は、好ましくは感光剤を含む。
感光剤は、光により活性種を発生して感光性樹脂組成物を硬化させることが可能なものである限り、特に限定されない。 (Photosensitizer)
The photosensitive resin composition of this embodiment preferably contains a photosensitive agent.
The photosensitive agent is not particularly limited as long as it can generate active species by light and cure the photosensitive resin composition.
感光剤は、好ましくは光ラジカル発生剤を含む。光ラジカル発生剤は、特に、多官能(メタ)アクリレート化合物を重合させるのに効果的である。
The photosensitizer preferably contains a photoradical generator. Photoradical generators are particularly effective in polymerizing polyfunctional (meth)acrylate compounds.
用いることができる光ラジカル発生剤は特に限定されず、公知のものを適宜用いることができる。
例えば、2,2-ジエトキシアセトフェノン、2,2-ジメトキシー2-フェニルアセトフェノン、1-ヒドロキシシクロヘキシルフェニルケトン、2-ヒドロキシ-2-メチル-1-フェニルプロパン-1-オン、1-〔4-(2-ヒドロキシエトキシ)フェニル〕-2-ヒドロキシ-2-メチル-1-プロパン-1-オン、2-ヒドロキシ-1-{4-〔4-(2-ヒドロキシ-2-メチルプロピオニル)ベンジル〕フェニル}-2-メチルプロパン-1-オン、2-メチル-1-(4-メチルチオフェニル)-2-モルフォリノプロパン1-オン、2-ベンジル-2-ジメチルアミノ-1-(4-モルフォリノフェニル)-ブタノン-1、2-(ジメチルアミノ)-2-〔(4-メチルフェニル)メチル〕-1-〔4-(4-モルホリニル)フェニル〕-1-ブタノン等のアルキルフェノン系化合物;ベンゾフェノン、4,4′-ビス(ジメチルアミノ)ベンゾフェノン、2-カルボキシベンゾフェノン等のベンゾフェノン系化合物;ベンゾインメチルエーテル、ベンゾインエチルエーテル、ベンゾインイソプロピルエーテル、ベンゾインイソブチルエーテ等のベンゾイン系化合物;チオキサントン、2-エチルチオキサントン、2-イソプロピルチオキサントン、2-クロロチオキサントン、2,4-ジメチルチオキサントン、2,4-ジエチルチオキサントン等のチオキサントン系化合物;2-(4-メトキシフェニル)-4,6-ビス(トリクロロメチル)-s-トリアジン、2-(4-メトキシナフチル)-4,6-ビス(トリクロロメチル)-s-トリアジン、2-(4-エトキシナフチル)-4,6-ビス(トリクロロメチル)-s-トリアジン、2-(4-エトキシカルボキニルナフチル)-4,6-ビス(トリクロロメチル)-s-トリアジン等のハロメチル化トリアジン系化合物;2-トリクロロメチル-5-(2′-ベンゾフリル)-1,3,4-オキサジアゾール、2-トリクロロメチル-5-〔β-(2′-ベンゾフリル)ビニル〕-1,3,4-オキサジアゾール、4-オキサジアゾール、2-トリクロロメチル-5-フリル-1,3,4-オキサジアゾール等のハロメチル化オキサジアゾール系化合物;2,2′-ビス(2-クロロフェニル)-4,4′,5,5′-テトラフェニル-1,2′-ビイミダゾール、2,2′-ビス(2,4-ジクロロフェニル)-4,4′,5,5′-テトラフェニル-1,2′-ビイミダゾール、2,2′-ビス(2,4,6-トリクロロフェニル)-4,4′,5,5′-テトラフェニル-1,2′-ビイミダゾール等のビイミダゾール系化合物;1,2-オクタンジオン,1-〔4-(フェニルチオ)フェニル〕-2-(O-ベンゾイルオキシム)、エタノン,1-〔9-エチル-6-(2-メチルベンゾイル)-9H-カルバゾール-3-イル〕-,1-(O-アセチルオキシム)等のオキシムエステル系化合物;ビス(η5-2,4-シクロペンタジエン-1-イル)-ビス(2,6-ジフルオロ-3-(1H-ピロール-1-イル)-フェニル)チタニウム等のチタノセン系化合物;p-ジメチルアミノ安息香酸、p-ジエチルアミノ安息香酸等の安息香酸エステル系化合物;9-フェニルアクリジン等のアクリジン系化合物;等を挙げることができる。これらの中でも、特にオキシムエステル系化合物を好ましく用いることができる。 The photoradical generator that can be used is not particularly limited, and known ones can be used as appropriate.
For example, 2,2-diethoxyacetophenone, 2,2-dimethoxy-2-phenylacetophenone, 1-hydroxycyclohexylphenylketone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, 1-[4-( 2-hydroxyethoxy)phenyl]-2-hydroxy-2-methyl-1-propan-1-one, 2-hydroxy-1-{4-[4-(2-hydroxy-2-methylpropionyl)benzyl]phenyl} -2-methylpropan-1-one, 2-methyl-1-(4-methylthiophenyl)-2-morpholinopropan-1-one, 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl) -butanone-1,2-(dimethylamino)-2-[(4-methylphenyl)methyl]-1-[4-(4-morpholinyl)phenyl]-1-butanone and other alkylphenone compounds; benzophenone, 4 , 4′-bis(dimethylamino)benzophenone, benzophenone compounds such as 2-carboxybenzophenone; benzoin compounds such as benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether; thioxanthone, 2-ethylthioxanthone, 2 -thioxanthone compounds such as isopropylthioxanthone, 2-chlorothioxanthone, 2,4-dimethylthioxanthone, and 2,4-diethylthioxanthone; 2-(4-methoxyphenyl)-4,6-bis(trichloromethyl)-s-triazine , 2-(4-methoxynaphthyl)-4,6-bis(trichloromethyl)-s-triazine, 2-(4-ethoxynaphthyl)-4,6-bis(trichloromethyl)-s-triazine, 2-( Halomethylated triazine compounds such as 4-ethoxycarbonylnaphthyl)-4,6-bis(trichloromethyl)-s-triazine; 2-trichloromethyl-5-(2'-benzofuryl)-1,3,4-oxa diazole, 2-trichloromethyl-5-[β-(2′-benzofuryl)vinyl]-1,3,4-oxadiazole, 4-oxadiazole, 2-trichloromethyl-5-furyl-1,3 Halomethylated oxadiazole compounds such as ,4-oxadiazole; 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetraphenyl-1,2'-biimidazole, 2 ,2′-bis(2,4-dichlorophenyl)-4,4′,5,5′- Tetraphenyl-1,2'-biimidazole, 2,2'-bis(2,4,6-trichlorophenyl)-4,4',5,5'-tetraphenyl-1,2'-biimidazole, etc. Biimidazole compounds; 1,2-octanedione, 1-[4-(phenylthio)phenyl]-2-(O-benzoyloxime), ethanone, 1-[9-ethyl-6-(2-methylbenzoyl)- 9H-carbazol-3-yl]-,1-(O-acetyloxime) and other oxime ester compounds; bis(η5-2,4-cyclopentadien-1-yl)-bis(2,6-difluoro-3 -(1H-pyrrol-1-yl)-phenyl) titanocene compounds such as titanium; benzoic acid ester compounds such as p-dimethylaminobenzoic acid and p-diethylaminobenzoic acid; acridine compounds such as 9-phenylacridine; etc. can be mentioned. Among these, oxime ester compounds can be preferably used.
例えば、2,2-ジエトキシアセトフェノン、2,2-ジメトキシー2-フェニルアセトフェノン、1-ヒドロキシシクロヘキシルフェニルケトン、2-ヒドロキシ-2-メチル-1-フェニルプロパン-1-オン、1-〔4-(2-ヒドロキシエトキシ)フェニル〕-2-ヒドロキシ-2-メチル-1-プロパン-1-オン、2-ヒドロキシ-1-{4-〔4-(2-ヒドロキシ-2-メチルプロピオニル)ベンジル〕フェニル}-2-メチルプロパン-1-オン、2-メチル-1-(4-メチルチオフェニル)-2-モルフォリノプロパン1-オン、2-ベンジル-2-ジメチルアミノ-1-(4-モルフォリノフェニル)-ブタノン-1、2-(ジメチルアミノ)-2-〔(4-メチルフェニル)メチル〕-1-〔4-(4-モルホリニル)フェニル〕-1-ブタノン等のアルキルフェノン系化合物;ベンゾフェノン、4,4′-ビス(ジメチルアミノ)ベンゾフェノン、2-カルボキシベンゾフェノン等のベンゾフェノン系化合物;ベンゾインメチルエーテル、ベンゾインエチルエーテル、ベンゾインイソプロピルエーテル、ベンゾインイソブチルエーテ等のベンゾイン系化合物;チオキサントン、2-エチルチオキサントン、2-イソプロピルチオキサントン、2-クロロチオキサントン、2,4-ジメチルチオキサントン、2,4-ジエチルチオキサントン等のチオキサントン系化合物;2-(4-メトキシフェニル)-4,6-ビス(トリクロロメチル)-s-トリアジン、2-(4-メトキシナフチル)-4,6-ビス(トリクロロメチル)-s-トリアジン、2-(4-エトキシナフチル)-4,6-ビス(トリクロロメチル)-s-トリアジン、2-(4-エトキシカルボキニルナフチル)-4,6-ビス(トリクロロメチル)-s-トリアジン等のハロメチル化トリアジン系化合物;2-トリクロロメチル-5-(2′-ベンゾフリル)-1,3,4-オキサジアゾール、2-トリクロロメチル-5-〔β-(2′-ベンゾフリル)ビニル〕-1,3,4-オキサジアゾール、4-オキサジアゾール、2-トリクロロメチル-5-フリル-1,3,4-オキサジアゾール等のハロメチル化オキサジアゾール系化合物;2,2′-ビス(2-クロロフェニル)-4,4′,5,5′-テトラフェニル-1,2′-ビイミダゾール、2,2′-ビス(2,4-ジクロロフェニル)-4,4′,5,5′-テトラフェニル-1,2′-ビイミダゾール、2,2′-ビス(2,4,6-トリクロロフェニル)-4,4′,5,5′-テトラフェニル-1,2′-ビイミダゾール等のビイミダゾール系化合物;1,2-オクタンジオン,1-〔4-(フェニルチオ)フェニル〕-2-(O-ベンゾイルオキシム)、エタノン,1-〔9-エチル-6-(2-メチルベンゾイル)-9H-カルバゾール-3-イル〕-,1-(O-アセチルオキシム)等のオキシムエステル系化合物;ビス(η5-2,4-シクロペンタジエン-1-イル)-ビス(2,6-ジフルオロ-3-(1H-ピロール-1-イル)-フェニル)チタニウム等のチタノセン系化合物;p-ジメチルアミノ安息香酸、p-ジエチルアミノ安息香酸等の安息香酸エステル系化合物;9-フェニルアクリジン等のアクリジン系化合物;等を挙げることができる。これらの中でも、特にオキシムエステル系化合物を好ましく用いることができる。 The photoradical generator that can be used is not particularly limited, and known ones can be used as appropriate.
For example, 2,2-diethoxyacetophenone, 2,2-dimethoxy-2-phenylacetophenone, 1-hydroxycyclohexylphenylketone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, 1-[4-( 2-hydroxyethoxy)phenyl]-2-hydroxy-2-methyl-1-propan-1-one, 2-hydroxy-1-{4-[4-(2-hydroxy-2-methylpropionyl)benzyl]phenyl} -2-methylpropan-1-one, 2-methyl-1-(4-methylthiophenyl)-2-morpholinopropan-1-one, 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl) -butanone-1,2-(dimethylamino)-2-[(4-methylphenyl)methyl]-1-[4-(4-morpholinyl)phenyl]-1-butanone and other alkylphenone compounds; benzophenone, 4 , 4′-bis(dimethylamino)benzophenone, benzophenone compounds such as 2-carboxybenzophenone; benzoin compounds such as benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether; thioxanthone, 2-ethylthioxanthone, 2 -thioxanthone compounds such as isopropylthioxanthone, 2-chlorothioxanthone, 2,4-dimethylthioxanthone, and 2,4-diethylthioxanthone; 2-(4-methoxyphenyl)-4,6-bis(trichloromethyl)-s-triazine , 2-(4-methoxynaphthyl)-4,6-bis(trichloromethyl)-s-triazine, 2-(4-ethoxynaphthyl)-4,6-bis(trichloromethyl)-s-triazine, 2-( Halomethylated triazine compounds such as 4-ethoxycarbonylnaphthyl)-4,6-bis(trichloromethyl)-s-triazine; 2-trichloromethyl-5-(2'-benzofuryl)-1,3,4-oxa diazole, 2-trichloromethyl-5-[β-(2′-benzofuryl)vinyl]-1,3,4-oxadiazole, 4-oxadiazole, 2-trichloromethyl-5-furyl-1,3 Halomethylated oxadiazole compounds such as ,4-oxadiazole; 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetraphenyl-1,2'-biimidazole, 2 ,2′-bis(2,4-dichlorophenyl)-4,4′,5,5′- Tetraphenyl-1,2'-biimidazole, 2,2'-bis(2,4,6-trichlorophenyl)-4,4',5,5'-tetraphenyl-1,2'-biimidazole, etc. Biimidazole compounds; 1,2-octanedione, 1-[4-(phenylthio)phenyl]-2-(O-benzoyloxime), ethanone, 1-[9-ethyl-6-(2-methylbenzoyl)- 9H-carbazol-3-yl]-,1-(O-acetyloxime) and other oxime ester compounds; bis(η5-2,4-cyclopentadien-1-yl)-bis(2,6-difluoro-3 -(1H-pyrrol-1-yl)-phenyl) titanocene compounds such as titanium; benzoic acid ester compounds such as p-dimethylaminobenzoic acid and p-diethylaminobenzoic acid; acridine compounds such as 9-phenylacridine; etc. can be mentioned. Among these, oxime ester compounds can be preferably used.
感光剤を用いる場合、1のみの感光剤を用いてもよいし、2以上の感光剤を用いてもよい。
感光剤の含有量は、多官能(メタ)アクリレート化合物100質量部に対して、例えば1~30質量部であり、好ましくは5~20質量部である。 When using a photosensitive agent, only one photosensitive agent may be used, or two or more photosensitive agents may be used.
The content of the photosensitizer is, for example, 1 to 30 parts by weight, preferably 5 to 20 parts by weight, per 100 parts by weight of the polyfunctional (meth)acrylate compound.
感光剤の含有量は、多官能(メタ)アクリレート化合物100質量部に対して、例えば1~30質量部であり、好ましくは5~20質量部である。 When using a photosensitive agent, only one photosensitive agent may be used, or two or more photosensitive agents may be used.
The content of the photosensitizer is, for example, 1 to 30 parts by weight, preferably 5 to 20 parts by weight, per 100 parts by weight of the polyfunctional (meth)acrylate compound.
(熱ラジカル開始剤)
本実施形態の感光性樹脂組成物は、熱ラジカル開始剤を含んでもよい。
感光性樹脂組成物が添加剤として多官能(メタ)アクリル化合物を含有する場合、熱ラジカル開始剤を用いることにより、多官能(メタ)アクリル化合物の重合反応が促進され、硬化膜の耐熱性をより高める、かつ/または、硬化膜の耐薬品性(有機溶剤などに対する耐性)を高めることができる。 (thermal radical initiator)
The photosensitive resin composition of this embodiment may contain a thermal radical initiator.
When the photosensitive resin composition contains a polyfunctional (meth)acrylic compound as an additive, the use of a thermal radical initiator accelerates the polymerization reaction of the polyfunctional (meth)acrylic compound and improves the heat resistance of the cured film. and/or the chemical resistance (resistance to organic solvents and the like) of the cured film can be increased.
本実施形態の感光性樹脂組成物は、熱ラジカル開始剤を含んでもよい。
感光性樹脂組成物が添加剤として多官能(メタ)アクリル化合物を含有する場合、熱ラジカル開始剤を用いることにより、多官能(メタ)アクリル化合物の重合反応が促進され、硬化膜の耐熱性をより高める、かつ/または、硬化膜の耐薬品性(有機溶剤などに対する耐性)を高めることができる。 (thermal radical initiator)
The photosensitive resin composition of this embodiment may contain a thermal radical initiator.
When the photosensitive resin composition contains a polyfunctional (meth)acrylic compound as an additive, the use of a thermal radical initiator accelerates the polymerization reaction of the polyfunctional (meth)acrylic compound and improves the heat resistance of the cured film. and/or the chemical resistance (resistance to organic solvents and the like) of the cured film can be increased.
熱ラジカル開始剤は、好ましくは、有機過酸化物を含む。有機過酸化物としては、オクタノイルパーオキシド、ラウロイルパーオキシド、ステアロイルパーオキシド、1,1,3,3-テトラメチルブチルパーオキシ2-エチルヘキサノエート、シュウ酸パーオキシド、2,5-ジメチル-2,5-ジ(2-エチルヘキサノイルパーオキシ)ヘキサン、1-シクロヘキシル-1-メチルエチルパーオキシ2-エチルヘキサノエート、t-ヘキシルパーオキシ2-エチルヘキサノエート、t-ブチルパーオキシ2-エチルヘキサノエート、m-トルイルパーオキシド、ベンゾイルパーオキシド、ベンゾイルパーオキシド、メチルエチルケトンパーオキシド、アセチルパーオキシド、t-ブチルヒドロパーオキシド、ジ-t-ブチルパーオキシド、クメンヒドロパーオキシド、ジクミルパーオキシド、t-ブチルパーベンゾエート、パラクロロベンゾイルパーオキシド、シクロヘキサノンパーオキシド、などを挙げることができる。
The thermal radical initiator preferably contains an organic peroxide. Organic peroxides include octanoyl peroxide, lauroyl peroxide, stearoyl peroxide, 1,1,3,3-tetramethylbutylperoxy 2-ethylhexanoate, oxalic acid peroxide, 2,5-dimethyl- 2,5-di(2-ethylhexanoylperoxy)hexane, 1-cyclohexyl-1-methylethylperoxy 2-ethylhexanoate, t-hexylperoxy 2-ethylhexanoate, t-butylperoxy 2-ethylhexanoate, m-toluyl peroxide, benzoyl peroxide, benzoyl peroxide, methyl ethyl ketone peroxide, acetyl peroxide, t-butyl hydroperoxide, di-t-butyl peroxide, cumene hydroperoxide, dicyclo Examples include mill peroxide, t-butyl perbenzoate, parachlorobenzoyl peroxide, cyclohexanone peroxide, and the like.
熱ラジカル開始剤を用いる場合、1のみの熱ラジカル開始剤を用いてもよいし、2以上の熱ラジカル開始剤を用いてもよい。
熱ラジカル開始剤を用いる場合、その量は、多官能(メタ)アクリル化合物100質量部に対して、好ましくは0.1~30質量部、より好ましくは1~20質量部である。 When a thermal radical initiator is used, only one thermal radical initiator may be used, or two or more thermal radical initiators may be used.
When a thermal radical initiator is used, its amount is preferably 0.1 to 30 parts by weight, more preferably 1 to 20 parts by weight, based on 100 parts by weight of the polyfunctional (meth)acrylic compound.
熱ラジカル開始剤を用いる場合、その量は、多官能(メタ)アクリル化合物100質量部に対して、好ましくは0.1~30質量部、より好ましくは1~20質量部である。 When a thermal radical initiator is used, only one thermal radical initiator may be used, or two or more thermal radical initiators may be used.
When a thermal radical initiator is used, its amount is preferably 0.1 to 30 parts by weight, more preferably 1 to 20 parts by weight, based on 100 parts by weight of the polyfunctional (meth)acrylic compound.
(エポキシ樹脂)
(Epoxy resin)
本実施形態の感光性樹脂組成物は、エポキシ樹脂を含んでもよい。エポキシ樹脂は、樹脂(A)と結合を形成すると考えられ、このようにして形成された結合により、硬化膜の機械物性(引張り伸びなど)を高めることが可能である。
The photosensitive resin composition of this embodiment may contain an epoxy resin. The epoxy resin is believed to form a bond with the resin (A), and the bond thus formed can enhance the mechanical properties (tensile elongation, etc.) of the cured film.
エポキシ樹脂の具体例としては、以下を挙げることができる。もちろん、エポキシ樹脂はこれらのみに限定されない。
ビスフェノールA型エポキシ樹脂、ビスフェノールF型エポキシ樹脂、ビスフェノールE型エポキシ樹脂、ビスフェノールS型エポキシ樹脂、水添ビスフェノールA型エポキシ樹脂、ビスフェノールM型エポキシ樹脂(4,4'-(1,3-フェニレンジイソプリジエン)ビスフェノール型エポキシ樹脂)、ビスフェノールP型エポキシ樹脂(4,4'-(1,4-フェニレンジイソプリジエン)ビスフェノール型エポキシ樹脂)、ビスフェノールZ型エポキシ樹脂(4,4'-シクロヘキシジエンビスフェノール型エポキシ樹脂)、テトラメチルビスフェノールF型エポキシ樹脂などのビスフェノール型エポキシ樹脂;フェノールノボラック型エポキシ樹脂、臭素化フェノールノボラック型エポキシ樹脂、クレゾールノボラック型エポキシ樹脂、テトラフェノール基エタン型ノボラック型エポキシ樹脂、縮合環芳香族炭化水素構造を有するノボラック型エポキシ樹脂などのノボラック型エポキシ樹脂;ビフェニル型エポキシ樹脂;キシリレン型エポキシ樹脂、ビフェニルアラルキル型エポキシ樹脂などのアラルキル型エポキシ樹脂;ナフチレンエーテル型エポキシ樹脂、ナフトール型エポキシ樹脂、ナフタレン型エポキシ樹脂、ナフタレンジオール型エポキシ樹脂、2~4官能エポキシ型ナフタレン樹脂、ビナフチル型エポキシ樹脂、ナフタレンアラルキル型エポキシ樹脂などのナフタレン骨格を有するエポキシ樹脂;アントラセン型エポキシ樹脂;フェノキシ型エポキシ樹脂;ジシクロペンタジエン型エポキシ樹脂;ノルボルネン型エポキシ樹脂;アダマンタン型エポキシ樹脂;フルオレン型エポキシ樹脂、リン含有エポキシ樹脂、脂環式エポキシ樹脂、脂肪族鎖状エポキシ樹脂、ビスフェノールAノボラック型エポキシ樹脂、ビキシレノール型エポキシ樹脂、トリヒドロキシフェニルメタン型エポキシ樹脂、スチルベン型エポキシ樹脂、テトラフェニロールエタン型エポキシ樹脂、トリグリシジルイソシアヌレートなどの複素環式エポキシ樹脂;N,N,N',N'-テトラグリシジルメタキシレンジアミン、N,N,N',N'-テトラグリシジルビスアミノメチルシクロヘキサン、N,N-ジグリシジルアニリンなどのグリシジルアミン類や、グリシジル(メタ)アクリレートとエチレン性不飽和二重結合を有する化合物との共重合物;ブタジエン構造を有するエポキシ樹脂;ビスフェノールのジグリシジルエーテル化物;ナフタレンジオールのジグリシジルエーテル化物;フェノール類のグリシジルエーテル化物など。 Specific examples of epoxy resins include the following. Of course, epoxy resins are not limited to these.
Bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol E type epoxy resin, bisphenol S type epoxy resin, hydrogenated bisphenol A type epoxy resin, bisphenol M type epoxy resin (4,4'-(1,3-phenylene isopridien) bisphenol type epoxy resin), bisphenol P type epoxy resin (4,4'-(1,4-phenylenediisopridiene) bisphenol type epoxy resin), bisphenol Z type epoxy resin (4,4'-cyclohexane Bisphenol-type epoxy resins such as cydiene bisphenol-type epoxy resin) and tetramethylbisphenol F-type epoxy resin; Resins, novolac type epoxy resins such as novolak type epoxy resins having a condensed ring aromatic hydrocarbon structure; biphenyl type epoxy resins; xylylene type epoxy resins, aralkyl type epoxy resins such as biphenyl aralkyl type epoxy resins; naphthylene ether type epoxy resins , naphthol-type epoxy resin, naphthalene-type epoxy resin, naphthalenediol-type epoxy resin, bi- to tetra-functional epoxy-type naphthalene resin, binaphthyl-type epoxy resin, naphthalene aralkyl-type epoxy resin, etc. Epoxy resins having a naphthalene skeleton; anthracene-type epoxy resin; Phenoxy type epoxy resin; dicyclopentadiene type epoxy resin; norbornene type epoxy resin; adamantane type epoxy resin; fluorene type epoxy resin, phosphorus-containing epoxy resin, alicyclic epoxy resin, aliphatic chain epoxy resin, bisphenol A novolac type epoxy Heterocyclic epoxy resins such as resins, bixylenol-type epoxy resins, trihydroxyphenylmethane-type epoxy resins, stilbene-type epoxy resins, tetraphenylolethane-type epoxy resins, and triglycidyl isocyanurate; - Glycidylamines such as tetraglycidyl metaxylenediamine, N,N,N',N'-tetraglycidylbisaminomethylcyclohexane, N,N-diglycidylaniline, glycidyl (meth)acrylate and ethylenically unsaturated double Copolymer with a compound having a bond; Epoxy resin having a butadiene structure; Diglycidyl ether of bisphenol telluride; naphthalenediol diglycidyl ether; phenol glycidyl ether;
ビスフェノールA型エポキシ樹脂、ビスフェノールF型エポキシ樹脂、ビスフェノールE型エポキシ樹脂、ビスフェノールS型エポキシ樹脂、水添ビスフェノールA型エポキシ樹脂、ビスフェノールM型エポキシ樹脂(4,4'-(1,3-フェニレンジイソプリジエン)ビスフェノール型エポキシ樹脂)、ビスフェノールP型エポキシ樹脂(4,4'-(1,4-フェニレンジイソプリジエン)ビスフェノール型エポキシ樹脂)、ビスフェノールZ型エポキシ樹脂(4,4'-シクロヘキシジエンビスフェノール型エポキシ樹脂)、テトラメチルビスフェノールF型エポキシ樹脂などのビスフェノール型エポキシ樹脂;フェノールノボラック型エポキシ樹脂、臭素化フェノールノボラック型エポキシ樹脂、クレゾールノボラック型エポキシ樹脂、テトラフェノール基エタン型ノボラック型エポキシ樹脂、縮合環芳香族炭化水素構造を有するノボラック型エポキシ樹脂などのノボラック型エポキシ樹脂;ビフェニル型エポキシ樹脂;キシリレン型エポキシ樹脂、ビフェニルアラルキル型エポキシ樹脂などのアラルキル型エポキシ樹脂;ナフチレンエーテル型エポキシ樹脂、ナフトール型エポキシ樹脂、ナフタレン型エポキシ樹脂、ナフタレンジオール型エポキシ樹脂、2~4官能エポキシ型ナフタレン樹脂、ビナフチル型エポキシ樹脂、ナフタレンアラルキル型エポキシ樹脂などのナフタレン骨格を有するエポキシ樹脂;アントラセン型エポキシ樹脂;フェノキシ型エポキシ樹脂;ジシクロペンタジエン型エポキシ樹脂;ノルボルネン型エポキシ樹脂;アダマンタン型エポキシ樹脂;フルオレン型エポキシ樹脂、リン含有エポキシ樹脂、脂環式エポキシ樹脂、脂肪族鎖状エポキシ樹脂、ビスフェノールAノボラック型エポキシ樹脂、ビキシレノール型エポキシ樹脂、トリヒドロキシフェニルメタン型エポキシ樹脂、スチルベン型エポキシ樹脂、テトラフェニロールエタン型エポキシ樹脂、トリグリシジルイソシアヌレートなどの複素環式エポキシ樹脂;N,N,N',N'-テトラグリシジルメタキシレンジアミン、N,N,N',N'-テトラグリシジルビスアミノメチルシクロヘキサン、N,N-ジグリシジルアニリンなどのグリシジルアミン類や、グリシジル(メタ)アクリレートとエチレン性不飽和二重結合を有する化合物との共重合物;ブタジエン構造を有するエポキシ樹脂;ビスフェノールのジグリシジルエーテル化物;ナフタレンジオールのジグリシジルエーテル化物;フェノール類のグリシジルエーテル化物など。 Specific examples of epoxy resins include the following. Of course, epoxy resins are not limited to these.
Bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol E type epoxy resin, bisphenol S type epoxy resin, hydrogenated bisphenol A type epoxy resin, bisphenol M type epoxy resin (4,4'-(1,3-phenylene isopridien) bisphenol type epoxy resin), bisphenol P type epoxy resin (4,4'-(1,4-phenylenediisopridiene) bisphenol type epoxy resin), bisphenol Z type epoxy resin (4,4'-cyclohexane Bisphenol-type epoxy resins such as cydiene bisphenol-type epoxy resin) and tetramethylbisphenol F-type epoxy resin; Resins, novolac type epoxy resins such as novolak type epoxy resins having a condensed ring aromatic hydrocarbon structure; biphenyl type epoxy resins; xylylene type epoxy resins, aralkyl type epoxy resins such as biphenyl aralkyl type epoxy resins; naphthylene ether type epoxy resins , naphthol-type epoxy resin, naphthalene-type epoxy resin, naphthalenediol-type epoxy resin, bi- to tetra-functional epoxy-type naphthalene resin, binaphthyl-type epoxy resin, naphthalene aralkyl-type epoxy resin, etc. Epoxy resins having a naphthalene skeleton; anthracene-type epoxy resin; Phenoxy type epoxy resin; dicyclopentadiene type epoxy resin; norbornene type epoxy resin; adamantane type epoxy resin; fluorene type epoxy resin, phosphorus-containing epoxy resin, alicyclic epoxy resin, aliphatic chain epoxy resin, bisphenol A novolac type epoxy Heterocyclic epoxy resins such as resins, bixylenol-type epoxy resins, trihydroxyphenylmethane-type epoxy resins, stilbene-type epoxy resins, tetraphenylolethane-type epoxy resins, and triglycidyl isocyanurate; - Glycidylamines such as tetraglycidyl metaxylenediamine, N,N,N',N'-tetraglycidylbisaminomethylcyclohexane, N,N-diglycidylaniline, glycidyl (meth)acrylate and ethylenically unsaturated double Copolymer with a compound having a bond; Epoxy resin having a butadiene structure; Diglycidyl ether of bisphenol telluride; naphthalenediol diglycidyl ether; phenol glycidyl ether;
エポキシ樹脂を添加剤として用いる場合、その量は、樹脂(A)100質量部に対して、例えば0.5~100質量部、好ましくは1~50質量部、さらに好ましくは3~20質量部である。
When an epoxy resin is used as an additive, its amount is, for example, 0.5 to 100 parts by mass, preferably 1 to 50 parts by mass, more preferably 3 to 20 parts by mass, relative to 100 parts by mass of the resin (A). be.
添加剤としてエポキシ樹脂を用いる場合、1のみのエポキシ樹脂を用いてもよいし、2以上のエポキシ樹脂を併用してもよい。
When an epoxy resin is used as an additive, only one epoxy resin may be used, or two or more epoxy resins may be used together.
(硬化触媒)
本実施形態の感光性樹脂組成物は、硬化触媒を含んでもよい。
感光性樹脂組成物が添加剤としてエポキシ樹脂を含有する場合、硬化触媒を用いることにより、エポキシ樹脂の重合反応が促進され、例えば硬化膜の引張り伸び率を一層向上させることができる。 (Curing catalyst)
The photosensitive resin composition of this embodiment may contain a curing catalyst.
When the photosensitive resin composition contains an epoxy resin as an additive, the use of a curing catalyst promotes the polymerization reaction of the epoxy resin, and can further improve, for example, the tensile elongation of the cured film.
本実施形態の感光性樹脂組成物は、硬化触媒を含んでもよい。
感光性樹脂組成物が添加剤としてエポキシ樹脂を含有する場合、硬化触媒を用いることにより、エポキシ樹脂の重合反応が促進され、例えば硬化膜の引張り伸び率を一層向上させることができる。 (Curing catalyst)
The photosensitive resin composition of this embodiment may contain a curing catalyst.
When the photosensitive resin composition contains an epoxy resin as an additive, the use of a curing catalyst promotes the polymerization reaction of the epoxy resin, and can further improve, for example, the tensile elongation of the cured film.
硬化触媒としては、エポキシ樹脂の硬化触媒(しばしば、硬化促進剤とも呼ばれる)として知られている化合物を挙げることができる。例えば、1,8-ジアザビシクロ[5,4,0]ウンデセン-7等のジアザビシクロアルケンおよびその誘導体;トリブチルアミン、ベンジルジメチルアミン等のアミン系化合物;2-メチルイミダゾール等のイミダゾール化合物;トリフェニルホスフィン、メチルジフェニルホスフィン等の有機ホスフィン類;テトラフェニルホスホニウム・テトラフェニルボレート、テトラフェニルホスホニウム・テトラ安息香酸ボレート、テトラフェニルホスホニウム・テトラナフトイックアシッドボレート、テトラフェニルホスホニウム・テトラナフトイルオキシボレート、テトラフェニルホスホニウム・テトラナフチルオキシボレート、テトラフェニルホスホニウム・4,4'-スルフォニルジフェノラート等のテトラ置換ホスホニウム塩;ベンゾキノンをアダクトしたトリフェニルホスフィン等が挙げられる。なかでも、有機ホスフィン類が好ましく挙げられる。
Curing catalysts include compounds known as curing catalysts for epoxy resins (often called curing accelerators). For example, diazabicycloalkenes such as 1,8-diazabicyclo[5,4,0]undecene-7 and derivatives thereof; amine compounds such as tributylamine and benzyldimethylamine; imidazole compounds such as 2-methylimidazole; triphenyl Organic phosphines such as phosphine and methyldiphenylphosphine; tetra-substituted phosphonium salts such as phosphonium/tetranaphthyloxyborate and tetraphenylphosphonium/4,4'-sulfonyldiphenolate; and triphenylphosphine obtained by adducting benzoquinone. Among them, organic phosphines are preferred.
硬化触媒を用いる場合、その量は、エポキシ樹脂100質量部に対して、例えば1~80質量部、好ましくは5~50質量部、より好ましくは5~30質量部である。
When using a curing catalyst, its amount is, for example, 1 to 80 parts by mass, preferably 5 to 50 parts by mass, and more preferably 5 to 30 parts by mass with respect to 100 parts by mass of the epoxy resin.
(シランカップリング剤)
本実施形態の感光性樹脂組成物は、シランカップリング剤を含んでもよい。
シランカップリング剤を用いることにより、感光性樹脂組成物により形成される樹脂膜と、基材との密着性をより高めることができる。 (Silane coupling agent)
The photosensitive resin composition of this embodiment may contain a silane coupling agent.
By using the silane coupling agent, the adhesion between the resin film formed from the photosensitive resin composition and the substrate can be further enhanced.
本実施形態の感光性樹脂組成物は、シランカップリング剤を含んでもよい。
シランカップリング剤を用いることにより、感光性樹脂組成物により形成される樹脂膜と、基材との密着性をより高めることができる。 (Silane coupling agent)
The photosensitive resin composition of this embodiment may contain a silane coupling agent.
By using the silane coupling agent, the adhesion between the resin film formed from the photosensitive resin composition and the substrate can be further enhanced.
シランカップリング剤としては、例えば、アミノ基含有シランカップリング剤、エポキシ基含有シランカップリング剤、(メタ)アクリロイル基含有シランカップリング剤、メルカプト基含有シランカップリング剤、ビニル基含有シランカップリング剤、ウレイド基含有シランカップリング剤、スルフィド基含有シランカップリング剤、環状無水物構造を有するシランカップリング剤、などのシランカップリング剤を用いることができる。
Silane coupling agents include, for example, amino group-containing silane coupling agents, epoxy group-containing silane coupling agents, (meth)acryloyl group-containing silane coupling agents, mercapto group-containing silane coupling agents, and vinyl group-containing silane coupling agents. A silane coupling agent such as a ureido group-containing silane coupling agent, a sulfide group-containing silane coupling agent, and a silane coupling agent having a cyclic anhydride structure can be used.
本実施形態においては、樹脂(A)としてポリイミド樹脂が用いられる場合、環状無水物構造を有するシランカップリング剤が好ましく用いられる。詳細は不明だが、環状無水物構造は、ポリイミドの主鎖、側鎖および/または末端と反応しやすく、そのために特に良好な密着性向上効果が得られると推測される。
In this embodiment, when a polyimide resin is used as the resin (A), a silane coupling agent having a cyclic anhydride structure is preferably used. Although the details are unknown, it is speculated that the cyclic anhydride structure is likely to react with the main chain, side chains and/or terminals of the polyimide, and for this reason a particularly good effect of improving adhesion can be obtained.
シランカップリング剤が用いられる場合、単独で用いられてもよいし、2種以上のシランカップリング剤が併用されてもよい。
When a silane coupling agent is used, it may be used alone, or two or more silane coupling agents may be used in combination.
シランカップリング剤が用いられる場合、その使用量は、樹脂(A)の使用量を100質量部としたとき、例えば0.1~20質量部、好ましくは0.3~15質量部、より好ましく0.4~12質量部、さらに好ましくは0.5~10質量部である。
When a silane coupling agent is used, the amount used is, for example, 0.1 to 20 parts by mass, preferably 0.3 to 15 parts by mass, more preferably 0.3 to 15 parts by mass, when the amount of resin (A) used is 100 parts by mass. 0.4 to 12 parts by mass, more preferably 0.5 to 10 parts by mass.
(界面活性剤)
本実施形態の感光性樹脂組成物は、界面活性剤を含んでもよい。
界面活性剤を含むことにより、感光性樹脂組成物の塗布性や、感光性樹脂組成物により形成される樹脂膜の平坦性が一層高められる。
界面活性剤としては、フッ素系界面活性剤、シリコーン系界面活性剤、アルキル系界面活性剤、アクリル系界面活性剤などが挙げられる。
別観点として、界面活性剤は、非イオン性であることが好ましい。非イオン性の界面活性剤の使用は、例えば、組成物中の他成分との非意図的な反応を抑え、組成物の保存安定性を高める点で好ましい。 (Surfactant)
The photosensitive resin composition of this embodiment may contain a surfactant.
Inclusion of a surfactant further enhances the applicability of the photosensitive resin composition and the flatness of the resin film formed from the photosensitive resin composition.
Examples of surfactants include fluorine-based surfactants, silicone-based surfactants, alkyl-based surfactants, and acrylic surfactants.
From another point of view, the surfactant is preferably nonionic. The use of nonionic surfactants is preferable, for example, from the viewpoint of suppressing unintentional reactions with other components in the composition and enhancing the storage stability of the composition.
本実施形態の感光性樹脂組成物は、界面活性剤を含んでもよい。
界面活性剤を含むことにより、感光性樹脂組成物の塗布性や、感光性樹脂組成物により形成される樹脂膜の平坦性が一層高められる。
界面活性剤としては、フッ素系界面活性剤、シリコーン系界面活性剤、アルキル系界面活性剤、アクリル系界面活性剤などが挙げられる。
別観点として、界面活性剤は、非イオン性であることが好ましい。非イオン性の界面活性剤の使用は、例えば、組成物中の他成分との非意図的な反応を抑え、組成物の保存安定性を高める点で好ましい。 (Surfactant)
The photosensitive resin composition of this embodiment may contain a surfactant.
Inclusion of a surfactant further enhances the applicability of the photosensitive resin composition and the flatness of the resin film formed from the photosensitive resin composition.
Examples of surfactants include fluorine-based surfactants, silicone-based surfactants, alkyl-based surfactants, and acrylic surfactants.
From another point of view, the surfactant is preferably nonionic. The use of nonionic surfactants is preferable, for example, from the viewpoint of suppressing unintentional reactions with other components in the composition and enhancing the storage stability of the composition.
界面活性剤は、フッ素原子およびケイ素原子の少なくともいずれかを含む界面活性剤を含むことが好ましい。これにより、均一な樹脂膜を得られること(塗布性の向上)や、現像性の向上に加え、接着強度の向上にも寄与する。このような界面活性剤としては、例えば、フッ素原子およびケイ素原子の少なくともいずれかを含むノニオン系界面活性剤であることが好ましい。界面活性剤として使用可能な市販品としては、例えば、DIC株式会社製の「メガファック(登録商標)」シリーズの、F-251、F-253、F-281、F-430、F-477、F-551、F-552、F-553、F-554、F-555、F-556、F-557、F-558、F-559、F-560、F-561、F-562、F-563、F-565、F-568、F-569、F-570、F-572、F-574、F-575、F-576、R-40、R-40-LM、R-41、R-94等の、フッ素を含有するオリゴマー構造の界面活性剤、株式会社ネオス製のフタージェント250、フタージェント251等のフッ素含有ノニオン系界面活性剤、ワッカー・ケミー社製のSILFOAM(登録商標)シリーズ(例えばSD 100 TS、SD 670、SD 850、SD 860、SD 882)等のシリコーン系界面活性剤が挙げられる。
また、スリーエム社製のFC4430やFC4432なども、好ましい界面活性剤として挙げることができる。 The surfactant preferably contains a surfactant containing at least one of a fluorine atom and a silicon atom. This contributes to obtaining a uniform resin film (improvement of coatability), improvement of developability, and improvement of adhesive strength. Such a surfactant is preferably, for example, a nonionic surfactant containing at least one of a fluorine atom and a silicon atom. Examples of commercial products that can be used as surfactants include F-251, F-253, F-281, F-430, and F-477 of "Megafac (registered trademark)" series manufactured by DIC Corporation. F-551, F-552, F-553, F-554, F-555, F-556, F-557, F-558, F-559, F-560, F-561, F-562, F- 563, F-565, F-568, F-569, F-570, F-572, F-574, F-575, F-576, R-40, R-40-LM, R-41, R- 94, fluorine-containing oligomer structure surfactants, fluorine-containing nonionic surfactants such as Phthagent 250 and Phthagent 251 manufactured by Neos Co., Ltd., SILFOAM (registered trademark) series manufactured by Wacker Chemie ( Examples include silicone surfactants such as SD 100 TS, SD 670, SD 850, SD 860, SD 882).
In addition, FC4430 and FC4432 manufactured by 3M are also preferable surfactants.
また、スリーエム社製のFC4430やFC4432なども、好ましい界面活性剤として挙げることができる。 The surfactant preferably contains a surfactant containing at least one of a fluorine atom and a silicon atom. This contributes to obtaining a uniform resin film (improvement of coatability), improvement of developability, and improvement of adhesive strength. Such a surfactant is preferably, for example, a nonionic surfactant containing at least one of a fluorine atom and a silicon atom. Examples of commercial products that can be used as surfactants include F-251, F-253, F-281, F-430, and F-477 of "Megafac (registered trademark)" series manufactured by DIC Corporation. F-551, F-552, F-553, F-554, F-555, F-556, F-557, F-558, F-559, F-560, F-561, F-562, F- 563, F-565, F-568, F-569, F-570, F-572, F-574, F-575, F-576, R-40, R-40-LM, R-41, R- 94, fluorine-containing oligomer structure surfactants, fluorine-containing nonionic surfactants such as Phthagent 250 and Phthagent 251 manufactured by Neos Co., Ltd., SILFOAM (registered trademark) series manufactured by Wacker Chemie ( Examples include silicone surfactants such as SD 100 TS, SD 670, SD 850, SD 860, SD 882).
In addition, FC4430 and FC4432 manufactured by 3M are also preferable surfactants.
界面活性剤が用いられる場合、単独で用いられてもよいし、2種以上の界面活性剤を併用してもよい。
When a surfactant is used, it may be used alone, or two or more surfactants may be used in combination.
本実施形態の感光性樹脂組成物が界面活性剤を含む場合、その量は、樹脂(A)の含有量を100質量部としたとき、例えば0.001~1質量部、好ましくは0.005~0.5質量部である。
When the photosensitive resin composition of the present embodiment contains a surfactant, its amount is, for example, 0.001 to 1 part by mass, preferably 0.005, when the content of the resin (A) is 100 parts by mass. ~0.5 parts by mass.
(水)
本実施形態の感光性樹脂組成物は、水を含んでもよい。
水の存在により、例えば、シランカップリング剤の加水分解反応が進行しやすくなり、基材と硬化膜との密着性がより高まる傾向がある。 (water)
The photosensitive resin composition of this embodiment may contain water.
The presence of water, for example, facilitates the hydrolysis reaction of the silane coupling agent, and tends to further increase the adhesion between the substrate and the cured film.
本実施形態の感光性樹脂組成物は、水を含んでもよい。
水の存在により、例えば、シランカップリング剤の加水分解反応が進行しやすくなり、基材と硬化膜との密着性がより高まる傾向がある。 (water)
The photosensitive resin composition of this embodiment may contain water.
The presence of water, for example, facilitates the hydrolysis reaction of the silane coupling agent, and tends to further increase the adhesion between the substrate and the cured film.
本実施形態の感光性樹脂組成物が水を含む場合、その量は、感光性樹脂組成物の全固形分(不揮発成分)100質量部に対して、好ましくは0.1~5質量部、より好ましくは0.2~3質量部、さらに好ましくは0.5~2質量部である。
When the photosensitive resin composition of the present embodiment contains water, the amount is preferably 0.1 to 5 parts by weight, based on 100 parts by weight of the total solid content (non-volatile components) of the photosensitive resin composition. It is preferably 0.2 to 3 parts by mass, more preferably 0.5 to 2 parts by mass.
感光性樹脂組成物の水分量は、カールフィッシャー法により定量することができる。
The water content of the photosensitive resin composition can be quantified by the Karl Fischer method.
(溶剤/組成物の性状)
本実施形態の感光性樹脂組成物は、好ましくは溶剤を含む。これにより、基材(特に、段差を有する基材)に対して塗布法により感光性樹脂膜を容易に形成することができる。
溶剤は、通常、有機溶剤を含む。上述の各成分を溶解または分散可能で、かつ、各構成成分と実質的に化学反応しないものである限り、有機溶剤は特に限定されない。 (Solvent/composition properties)
The photosensitive resin composition of this embodiment preferably contains a solvent. This makes it possible to easily form a photosensitive resin film on a base material (particularly, a base material having steps) by a coating method.
A solvent usually contains an organic solvent. The organic solvent is not particularly limited as long as it can dissolve or disperse each component described above and does not substantially chemically react with each component.
本実施形態の感光性樹脂組成物は、好ましくは溶剤を含む。これにより、基材(特に、段差を有する基材)に対して塗布法により感光性樹脂膜を容易に形成することができる。
溶剤は、通常、有機溶剤を含む。上述の各成分を溶解または分散可能で、かつ、各構成成分と実質的に化学反応しないものである限り、有機溶剤は特に限定されない。 (Solvent/composition properties)
The photosensitive resin composition of this embodiment preferably contains a solvent. This makes it possible to easily form a photosensitive resin film on a base material (particularly, a base material having steps) by a coating method.
A solvent usually contains an organic solvent. The organic solvent is not particularly limited as long as it can dissolve or disperse each component described above and does not substantially chemically react with each component.
有機溶剤としては、例えば、アセトン、メチルエチルケトン、トルエン、プロピレングリコールメチルエチルエーテル、プロピレングリコールジメチルエーテル、プロピレングリコール1-モノメチルエーテル2-アセテート、ジエチレングリコールエチルメチルエーテル、ジエチレングリコールモノエチルエーテルアセテート、ジエチレングリコールモノブチルエーテルアセテート、ベンジルアルコール、プロピレンカーボネート、エチレングリコールジアセテート、プロピレングリコールジアセテート、プロピレングリコールモノメチルエーテルアセテート、ジプロプレングリコールメチル-n-プロピルエーテル、酢酸ブチル、γ-ブチロラクトン、乳酸メチル、乳酸エチル、乳酸ブチル等が挙げられる。これらは単独で用いても、複数組み合わせて用いてもよい。
Examples of organic solvents include acetone, methyl ethyl ketone, toluene, propylene glycol methyl ethyl ether, propylene glycol dimethyl ether, propylene glycol 1-monomethyl ether 2-acetate, diethylene glycol ethyl methyl ether, diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether acetate, benzyl Alcohol, propylene carbonate, ethylene glycol diacetate, propylene glycol diacetate, propylene glycol monomethyl ether acetate, dipropylene glycol methyl-n-propyl ether, butyl acetate, γ-butyrolactone, methyl lactate, ethyl lactate, butyl lactate and the like. . These may be used singly or in combination.
本実施形態の感光性樹脂組成物が溶剤を含む場合、本実施形態の感光性樹脂組成物は、通常、ワニス状である。本実施形態の感光性樹脂組成物がワニス状であることにより、塗布による均一な膜形成を行うことができる。また、本実施形態の感光性樹脂組成物は、ワニス状であり且つ少なくとも樹脂(A)が溶剤に溶解していることが好ましい。
When the photosensitive resin composition of the present embodiment contains a solvent, the photosensitive resin composition of the present embodiment is usually in the form of varnish. Since the photosensitive resin composition of the present embodiment is in the form of varnish, it is possible to form a uniform film by coating. Moreover, it is preferable that the photosensitive resin composition of the present embodiment is in the form of a varnish and that at least the resin (A) is dissolved in a solvent.
感光性樹脂組成物中の不揮発成分を「全固形分」とすると、溶剤を用いる場合は、感光性樹脂組成物中の全固形分の濃度が、好ましくは10~50質量%、より好ましくは20~45質量%となるように用いられる。この範囲とすることで、各成分を十分に溶解または分散させることができる。また、良好な塗布性を担保することができ、ひいてはスピンコート時の平坦性の良化にもつながる。さらに、不揮発成分の含有量を調整することにより、感光性樹脂組成物の粘度を適切に制御できる。
When the non-volatile component in the photosensitive resin composition is "total solid content", when a solvent is used, the concentration of the total solid content in the photosensitive resin composition is preferably 10 to 50% by mass, more preferably 20 It is used so as to be ∼45% by mass. By setting it as this range, each component can fully be melt|dissolved or dispersed. In addition, good coatability can be ensured, which in turn leads to improvement in flatness during spin coating. Furthermore, the viscosity of the photosensitive resin composition can be appropriately controlled by adjusting the content of the non-volatile component.
本実施形態の感光性樹脂組成物は、上記の成分に加えて、必要に応じて、上掲の成分以外の成分を含んでもよい。そのような成分としては、例えば、酸化防止剤、シリカ等の充填材、増感剤、フィルム化剤等が挙げられる。
In addition to the components described above, the photosensitive resin composition of the present embodiment may contain components other than those listed above, if necessary. Examples of such components include antioxidants, fillers such as silica, sensitizers, film-forming agents, and the like.
[樹脂膜]
本実施形態の樹脂膜は、上記の感光性樹脂組成物の硬化物から成る。 [Resin film]
The resin film of the present embodiment is made of a cured product of the above photosensitive resin composition.
本実施形態の樹脂膜は、上記の感光性樹脂組成物の硬化物から成る。 [Resin film]
The resin film of the present embodiment is made of a cured product of the above photosensitive resin composition.
例えば、電子装置の基材上に上記の感光性樹脂組成物を塗布し、硬化させ、樹脂膜を形成させることができる。
For example, the above photosensitive resin composition can be applied onto a base material of an electronic device and cured to form a resin film.
[電子装置]
本実施形態の電子装置は、上記の樹脂膜を備える。 [Electronic device]
The electronic device of this embodiment includes the resin film described above.
本実施形態の電子装置は、上記の樹脂膜を備える。 [Electronic device]
The electronic device of this embodiment includes the resin film described above.
本実施形態の電子装置は、下記の製造工程により製造することができる。
The electronic device of this embodiment can be manufactured by the following manufacturing process.
本実施形態の電子装置の製造工程は、
基材上に、上述の感光性樹脂組成物を用いて感光性樹脂膜を形成する膜形成工程と、
感光性樹脂膜を露光する露光工程と、
露光された感光性樹脂膜を現像する現像工程と、
を含む。
また、本実施形態の電子装置の製造方法は、上述の現像工程の後に、露光された感光性樹脂膜を加熱して硬化させる熱硬化工程を含むことが好ましい。これにより、耐熱性が良好な硬化膜を得ることができる。 The manufacturing process of the electronic device of this embodiment includes:
A film forming step of forming a photosensitive resin film on a substrate using the photosensitive resin composition described above;
an exposure step of exposing the photosensitive resin film;
a developing step of developing the exposed photosensitive resin film;
including.
Moreover, it is preferable that the method for manufacturing an electronic device of the present embodiment includes a thermosetting step of heating and curing the exposed photosensitive resin film after the above-described developing step. Thereby, a cured film having good heat resistance can be obtained.
基材上に、上述の感光性樹脂組成物を用いて感光性樹脂膜を形成する膜形成工程と、
感光性樹脂膜を露光する露光工程と、
露光された感光性樹脂膜を現像する現像工程と、
を含む。
また、本実施形態の電子装置の製造方法は、上述の現像工程の後に、露光された感光性樹脂膜を加熱して硬化させる熱硬化工程を含むことが好ましい。これにより、耐熱性が良好な硬化膜を得ることができる。 The manufacturing process of the electronic device of this embodiment includes:
A film forming step of forming a photosensitive resin film on a substrate using the photosensitive resin composition described above;
an exposure step of exposing the photosensitive resin film;
a developing step of developing the exposed photosensitive resin film;
including.
Moreover, it is preferable that the method for manufacturing an electronic device of the present embodiment includes a thermosetting step of heating and curing the exposed photosensitive resin film after the above-described developing step. Thereby, a cured film having good heat resistance can be obtained.
膜形成工程は、通常、基材上に感光性樹脂組成物を塗布することで行われる。膜形成工程は、スピンコーター、バーコーター、スプレー装置、インクジェット装置等を用いて行うことができる。
次の露光工程の前に、塗布された感光性樹脂組成物中の溶剤を乾燥させるなどの目的で、適切な加熱を行うことが好ましい。この際の加熱は、例えば80~150℃の温度で、1~60分間加熱することで行う。
乾燥後の感光性樹脂膜の厚みは、最終的に得ようとする電子デバイスの構造に応じて適宜変わるが、例えば1~100μm程度、具体的には1~50μm程度である。 The film forming step is usually performed by applying a photosensitive resin composition onto the substrate. The film forming step can be performed using a spin coater, bar coater, spray device, inkjet device, or the like.
Appropriate heating is preferably performed for the purpose of drying the solvent in the coated photosensitive resin composition before the next exposure step. The heating at this time is performed, for example, at a temperature of 80 to 150° C. for 1 to 60 minutes.
The thickness of the photosensitive resin film after drying varies depending on the structure of the final electronic device to be obtained.
次の露光工程の前に、塗布された感光性樹脂組成物中の溶剤を乾燥させるなどの目的で、適切な加熱を行うことが好ましい。この際の加熱は、例えば80~150℃の温度で、1~60分間加熱することで行う。
乾燥後の感光性樹脂膜の厚みは、最終的に得ようとする電子デバイスの構造に応じて適宜変わるが、例えば1~100μm程度、具体的には1~50μm程度である。 The film forming step is usually performed by applying a photosensitive resin composition onto the substrate. The film forming step can be performed using a spin coater, bar coater, spray device, inkjet device, or the like.
Appropriate heating is preferably performed for the purpose of drying the solvent in the coated photosensitive resin composition before the next exposure step. The heating at this time is performed, for example, at a temperature of 80 to 150° C. for 1 to 60 minutes.
The thickness of the photosensitive resin film after drying varies depending on the structure of the final electronic device to be obtained.
露光工程における露光量は、特に限定されない。100~2000mJ/cm2が好ましく、200~1000mJ/cm2がより好ましい。
露光に用いられる光源は特に限定されず、感光性樹脂組成物中の感光剤が反応する波長の光(例えばg線やi線)を発する光源であればよい。典型的には高圧水銀灯が用いられる。
必要に応じて、露光後ベークを施してもよい。露光後ベークの温度は、特に限定されない。好ましくは50~150℃、より好ましくは50~130℃、さらに好ましくは55~120℃、特に好ましくは60~110℃である。また、露光後ベークの時間は、好ましくは1~30分間、より好ましくは1~20分間、さらに好ましくは1~15分間である。
露光工程においては、フォトマスクを用いることができる。これにより、感光性樹脂組成物を用いて所望の「パターン」を形成することができる。 The amount of exposure in the exposure step is not particularly limited. 100 to 2000 mJ/cm 2 is preferred, and 200 to 1000 mJ/cm 2 is more preferred.
The light source used for exposure is not particularly limited as long as it emits light of a wavelength (eg, g-line or i-line) with which the photosensitive agent in the photosensitive resin composition reacts. A high pressure mercury lamp is typically used.
Post-exposure baking may be performed as necessary. The post-exposure baking temperature is not particularly limited. It is preferably 50 to 150°C, more preferably 50 to 130°C, still more preferably 55 to 120°C, and particularly preferably 60 to 110°C. Also, the post-exposure bake time is preferably 1 to 30 minutes, more preferably 1 to 20 minutes, still more preferably 1 to 15 minutes.
A photomask can be used in the exposure step. Thereby, a desired "pattern" can be formed using the photosensitive resin composition.
露光に用いられる光源は特に限定されず、感光性樹脂組成物中の感光剤が反応する波長の光(例えばg線やi線)を発する光源であればよい。典型的には高圧水銀灯が用いられる。
必要に応じて、露光後ベークを施してもよい。露光後ベークの温度は、特に限定されない。好ましくは50~150℃、より好ましくは50~130℃、さらに好ましくは55~120℃、特に好ましくは60~110℃である。また、露光後ベークの時間は、好ましくは1~30分間、より好ましくは1~20分間、さらに好ましくは1~15分間である。
露光工程においては、フォトマスクを用いることができる。これにより、感光性樹脂組成物を用いて所望の「パターン」を形成することができる。 The amount of exposure in the exposure step is not particularly limited. 100 to 2000 mJ/cm 2 is preferred, and 200 to 1000 mJ/cm 2 is more preferred.
The light source used for exposure is not particularly limited as long as it emits light of a wavelength (eg, g-line or i-line) with which the photosensitive agent in the photosensitive resin composition reacts. A high pressure mercury lamp is typically used.
Post-exposure baking may be performed as necessary. The post-exposure baking temperature is not particularly limited. It is preferably 50 to 150°C, more preferably 50 to 130°C, still more preferably 55 to 120°C, and particularly preferably 60 to 110°C. Also, the post-exposure bake time is preferably 1 to 30 minutes, more preferably 1 to 20 minutes, still more preferably 1 to 15 minutes.
A photomask can be used in the exposure step. Thereby, a desired "pattern" can be formed using the photosensitive resin composition.
現像工程における現像液としては、例えば、有機系現像液、水溶性現像液等が挙げられる。本実施形態においては、現像液は、有機溶剤を含有することが好ましい。より具体的には、現像液は、有機溶剤を主成分とする現像液(成分の95質量%以上が有機溶剤である現像液)であることが好ましい。有機溶剤を含有する現像液で現像することにより、アルカリ現像液(水系)で現像する場合よりも、現像液によるパターンの膨潤を抑えること等が可能になる。つまり、よりファインなパターンを得やすい。
Examples of the developer used in the development process include an organic developer and a water-soluble developer. In this embodiment, the developer preferably contains an organic solvent. More specifically, the developer is preferably a developer containing an organic solvent as a main component (a developer in which 95% by mass or more of the component is an organic solvent). By developing with a developer containing an organic solvent, swelling of the pattern due to the developer can be suppressed more than in the case of developing with an alkaline developer (aqueous). That is, it is easy to obtain a finer pattern.
現像液に使用可能な有機溶剤として具体的には、シクロペンタノンなどのケトン系溶剤、プロピレングリコールモノメチルエーテルアセテート(PGMEA)や酢酸ブチルなどのエステル系溶剤、プロピレングリコールモノメチルエーテルなどのエーテル系溶剤、等が挙げられる。
現像液としては、有機溶剤のみからなり、不可避的に含まれる不純物以外は含まない有機溶剤現像液を使用してもよい。不可避的に含まれる不純物としては、金属元素や水分があるが、電子デバイスの汚染防止などの観点からは不可避的に含まれる不純物は少ないに越したことは無い。 Specific examples of organic solvents that can be used in the developer include ketone solvents such as cyclopentanone, ester solvents such as propylene glycol monomethyl ether acetate (PGMEA) and butyl acetate, ether solvents such as propylene glycol monomethyl ether, etc.
As the developer, an organic solvent developer containing only an organic solvent and containing only unavoidable impurities may be used. Impurities that are unavoidably contained include metal elements and moisture, but from the viewpoint of preventing contamination of electronic devices, it is better that the impurities that are unavoidably contained are as small as possible.
現像液としては、有機溶剤のみからなり、不可避的に含まれる不純物以外は含まない有機溶剤現像液を使用してもよい。不可避的に含まれる不純物としては、金属元素や水分があるが、電子デバイスの汚染防止などの観点からは不可避的に含まれる不純物は少ないに越したことは無い。 Specific examples of organic solvents that can be used in the developer include ketone solvents such as cyclopentanone, ester solvents such as propylene glycol monomethyl ether acetate (PGMEA) and butyl acetate, ether solvents such as propylene glycol monomethyl ether, etc.
As the developer, an organic solvent developer containing only an organic solvent and containing only unavoidable impurities may be used. Impurities that are unavoidably contained include metal elements and moisture, but from the viewpoint of preventing contamination of electronic devices, it is better that the impurities that are unavoidably contained are as small as possible.
現像液を感光性樹脂膜に接触させる方法は特に限定されない。一般的に知られている、浸漬法、パドル法、スプレー法などを適宜適用することができる。
The method of bringing the developer into contact with the photosensitive resin film is not particularly limited. A generally known dipping method, paddle method, spray method, or the like can be appropriately applied.
現像工程の時間は、通常5~300秒程度、好ましくは10~120秒程度の範囲で、樹脂膜の膜厚や形成されるパターンの形状などに基づき適宜調整される。
The time for the development process is usually in the range of about 5 to 300 seconds, preferably about 10 to 120 seconds, and is appropriately adjusted based on the film thickness of the resin film, the shape of the pattern to be formed, and the like.
熱硬化工程の条件は特に限定されないが、例えば160~250℃程度の加熱温度で、30~240分程度とすることができる。
The conditions for the heat curing process are not particularly limited, but for example, the heating temperature can be about 160 to 250° C. for about 30 to 240 minutes.
以上、本発明の実施形態について述べたが、これらは本発明の例示であり、上記以外の様々な構成を採用することができる。また、本発明は上述の実施形態に限定されるものではなく、本発明の目的を達成できる範囲での変形、改良等は本発明に含まれる。
Although the embodiments of the present invention have been described above, these are examples of the present invention, and various configurations other than those described above can be adopted. Moreover, the present invention is not limited to the above-described embodiments, and includes modifications, improvements, etc. within the scope of achieving the object of the present invention.
本発明の実施態様を、実施例および比較例に基づき詳細に説明する。念のため述べておくと、本発明は実施例のみに限定されない。
Embodiments of the present invention will be described in detail based on examples and comparative examples. It should be noted that the invention is not limited to the examples only.
[各原料の合成]
<樹脂(A-1)の合成>
撹拌機および冷却管を備えた3Lのセパラブルフラスコに、2,2‘-ビス(トリフルオロメチル)ベンジジン304.2g(0.95モル)、4,4'-オキシジフタル酸二無水物310.22g(1.00モル)及びガンマブチロラクトン(GBL)1434gを加えて窒素雰囲気下で室温にて16時間反応し重合反応を行った。続いてオイルバスにて反応液温度を180℃まで上げ3時間反応を行ったのち室温まで冷却してポリイミド樹脂溶液を作成した。
続いて、反応液をイソプロパノール/水=4/7の混合溶液に撹拌しながら滴下し、樹脂固体を析出させた。得られた固体を荒濾過したのち、更にイソプロパノール/水=4/7で洗浄してポリイミドの白色固体を得た。得られた白色固体を200℃にて真空乾燥し、樹脂(A-1)を得た。
樹脂(A-1)のGPC測定による重量平均分子量(Mw)は50,000であった。 [Synthesis of each raw material]
<Synthesis of Resin (A-1)>
304.2 g (0.95 mol) of 2,2′-bis(trifluoromethyl)benzidine and 310.22 g of 4,4′-oxydiphthalic dianhydride were placed in a 3 L separable flask equipped with a stirrer and condenser. (1.00 mol) and 1434 g of gamma-butyrolactone (GBL) were added and reacted at room temperature for 16 hours under a nitrogen atmosphere to carry out a polymerization reaction. Subsequently, the temperature of the reaction liquid was raised to 180° C. in an oil bath and the reaction was carried out for 3 hours, and then cooled to room temperature to prepare a polyimide resin solution.
Subsequently, the reaction solution was added dropwise to a mixed solution of isopropanol/water=4/7 with stirring to precipitate a resin solid. After rough filtration of the obtained solid, it was further washed with isopropanol/water=4/7 to obtain a white polyimide solid. The resulting white solid was vacuum dried at 200° C. to obtain Resin (A-1).
Resin (A-1) had a weight average molecular weight (Mw) of 50,000 by GPC measurement.
<樹脂(A-1)の合成>
撹拌機および冷却管を備えた3Lのセパラブルフラスコに、2,2‘-ビス(トリフルオロメチル)ベンジジン304.2g(0.95モル)、4,4'-オキシジフタル酸二無水物310.22g(1.00モル)及びガンマブチロラクトン(GBL)1434gを加えて窒素雰囲気下で室温にて16時間反応し重合反応を行った。続いてオイルバスにて反応液温度を180℃まで上げ3時間反応を行ったのち室温まで冷却してポリイミド樹脂溶液を作成した。
続いて、反応液をイソプロパノール/水=4/7の混合溶液に撹拌しながら滴下し、樹脂固体を析出させた。得られた固体を荒濾過したのち、更にイソプロパノール/水=4/7で洗浄してポリイミドの白色固体を得た。得られた白色固体を200℃にて真空乾燥し、樹脂(A-1)を得た。
樹脂(A-1)のGPC測定による重量平均分子量(Mw)は50,000であった。 [Synthesis of each raw material]
<Synthesis of Resin (A-1)>
304.2 g (0.95 mol) of 2,2′-bis(trifluoromethyl)benzidine and 310.22 g of 4,4′-oxydiphthalic dianhydride were placed in a 3 L separable flask equipped with a stirrer and condenser. (1.00 mol) and 1434 g of gamma-butyrolactone (GBL) were added and reacted at room temperature for 16 hours under a nitrogen atmosphere to carry out a polymerization reaction. Subsequently, the temperature of the reaction liquid was raised to 180° C. in an oil bath and the reaction was carried out for 3 hours, and then cooled to room temperature to prepare a polyimide resin solution.
Subsequently, the reaction solution was added dropwise to a mixed solution of isopropanol/water=4/7 with stirring to precipitate a resin solid. After rough filtration of the obtained solid, it was further washed with isopropanol/water=4/7 to obtain a white polyimide solid. The resulting white solid was vacuum dried at 200° C. to obtain Resin (A-1).
Resin (A-1) had a weight average molecular weight (Mw) of 50,000 by GPC measurement.
<樹脂(A-2)の合成>
2Lのセパラブルフラスコに、GBL428g、4,4'-オキシジフタル酸二無水物155.11gおよび2-ヒドロキシエチルメタクリレート130.14gを入れ、室温でフラスコ内の成分を撹拌し完全に溶解させた。続いて室温下で攪拌しながらピリジン79.1gを加えて、更に室温で16時間撹拌した。 <Synthesis of resin (A-2)>
428 g of GBL, 155.11 g of 4,4′-oxydiphthalic dianhydride and 130.14 g of 2-hydroxyethyl methacrylate were placed in a 2 L separable flask, and the components in the flask were stirred at room temperature to dissolve completely. Subsequently, 79.1 g of pyridine was added while stirring at room temperature, and the mixture was further stirred at room temperature for 16 hours.
2Lのセパラブルフラスコに、GBL428g、4,4'-オキシジフタル酸二無水物155.11gおよび2-ヒドロキシエチルメタクリレート130.14gを入れ、室温でフラスコ内の成分を撹拌し完全に溶解させた。続いて室温下で攪拌しながらピリジン79.1gを加えて、更に室温で16時間撹拌した。 <Synthesis of resin (A-2)>
428 g of GBL, 155.11 g of 4,4′-oxydiphthalic dianhydride and 130.14 g of 2-hydroxyethyl methacrylate were placed in a 2 L separable flask, and the components in the flask were stirred at room temperature to dissolve completely. Subsequently, 79.1 g of pyridine was added while stirring at room temperature, and the mixture was further stirred at room temperature for 16 hours.
上記のようにして得られた溶液を氷冷下で冷却攪拌しながら、その溶液に、ジシクロヘキシルカルボジイミド206.3gをGBL206gに溶解した溶液を30分かけて加えた。続いて4,4'-ジアミノジフェニルエーテル120.1gおよびGBL240gを加え、更に室温で2時間攪拌を継続した。
反応終了後、エタノール30gを加えて1時間攪拌した。その後、GBL400gを加え更に撹拌し、生じた沈殿物をろ過により取り除いた。これによりポリアミド酸エステルの反応液を得た。
得られた反応液を、室温下で、大量の30質量%メタノール水溶液に撹拌しながら滴下し、樹脂を沈殿させた。得られた沈殿物を濾取し、真空乾燥することにより、樹脂(A-2)を得た。 While cooling and stirring the solution obtained as described above under ice-cooling, a solution of 206.3 g of dicyclohexylcarbodiimide dissolved in 206 g of GBL was added to the solution over 30 minutes. Subsequently, 120.1 g of 4,4'-diaminodiphenyl ether and 240 g of GBL were added, and stirring was continued at room temperature for 2 hours.
After completion of the reaction, 30 g of ethanol was added and stirred for 1 hour. After that, 400 g of GBL was added and further stirred, and the resulting precipitate was removed by filtration. Thus, a reaction solution of polyamic acid ester was obtained.
The resulting reaction solution was added dropwise to a large amount of 30% by mass methanol aqueous solution at room temperature while stirring to precipitate the resin. The resulting precipitate was collected by filtration and vacuum dried to obtain resin (A-2).
反応終了後、エタノール30gを加えて1時間攪拌した。その後、GBL400gを加え更に撹拌し、生じた沈殿物をろ過により取り除いた。これによりポリアミド酸エステルの反応液を得た。
得られた反応液を、室温下で、大量の30質量%メタノール水溶液に撹拌しながら滴下し、樹脂を沈殿させた。得られた沈殿物を濾取し、真空乾燥することにより、樹脂(A-2)を得た。 While cooling and stirring the solution obtained as described above under ice-cooling, a solution of 206.3 g of dicyclohexylcarbodiimide dissolved in 206 g of GBL was added to the solution over 30 minutes. Subsequently, 120.1 g of 4,4'-diaminodiphenyl ether and 240 g of GBL were added, and stirring was continued at room temperature for 2 hours.
After completion of the reaction, 30 g of ethanol was added and stirred for 1 hour. After that, 400 g of GBL was added and further stirred, and the resulting precipitate was removed by filtration. Thus, a reaction solution of polyamic acid ester was obtained.
The resulting reaction solution was added dropwise to a large amount of 30% by mass methanol aqueous solution at room temperature while stirring to precipitate the resin. The resulting precipitate was collected by filtration and vacuum dried to obtain resin (A-2).
<化合物(C-1)の合成>
撹拌装置付きのセパラブルフラスコに、メタクリル酸グリシジル142.15g(1.00mol)、GBL589gを仕込み、室温で撹拌溶解した。更に攪拌しながら5-メルカプト-1-メチルテトラゾール110.3g(0.95mol)を添加した。次いでオイルバスにて溶液を60℃まで加熱し、更に60℃で6時間反応を行い、化合物(C-1)の30%GBL溶液を得た。 <Synthesis of Compound (C-1)>
A separable flask equipped with a stirrer was charged with 142.15 g (1.00 mol) of glycidyl methacrylate and 589 g of GBL, which were stirred and dissolved at room temperature. Further, 110.3 g (0.95 mol) of 5-mercapto-1-methyltetrazole was added while stirring. Then, the solution was heated to 60° C. in an oil bath and further reacted at 60° C. for 6 hours to obtain a 30% GBL solution of compound (C-1).
撹拌装置付きのセパラブルフラスコに、メタクリル酸グリシジル142.15g(1.00mol)、GBL589gを仕込み、室温で撹拌溶解した。更に攪拌しながら5-メルカプト-1-メチルテトラゾール110.3g(0.95mol)を添加した。次いでオイルバスにて溶液を60℃まで加熱し、更に60℃で6時間反応を行い、化合物(C-1)の30%GBL溶液を得た。 <Synthesis of Compound (C-1)>
A separable flask equipped with a stirrer was charged with 142.15 g (1.00 mol) of glycidyl methacrylate and 589 g of GBL, which were stirred and dissolved at room temperature. Further, 110.3 g (0.95 mol) of 5-mercapto-1-methyltetrazole was added while stirring. Then, the solution was heated to 60° C. in an oil bath and further reacted at 60° C. for 6 hours to obtain a 30% GBL solution of compound (C-1).
<化合物(C-2)の合成>
撹拌装置付きのセパラブルフラスコに、4-ヒドロキシブチルアクリレートグリシジルエーテル200.23g(1.00mol)、GBL691gを仕込み、室温で撹拌溶解した。更に攪拌しながら3-メルカプト-1,2,4-トリアゾール96.07g(0.95mol)を添加した。次いでオイルバスにて溶液を60℃まで加熱し、更に60℃で6時間反応を行い、化合物(C-2)の30%GBL溶液を得た。 <Synthesis of compound (C-2)>
A separable flask equipped with a stirrer was charged with 200.23 g (1.00 mol) of 4-hydroxybutyl acrylate glycidyl ether and 691 g of GBL, and dissolved with stirring at room temperature. Further, 96.07 g (0.95 mol) of 3-mercapto-1,2,4-triazole was added while stirring. Then, the solution was heated to 60° C. in an oil bath and further reacted at 60° C. for 6 hours to obtain a 30% GBL solution of compound (C-2).
撹拌装置付きのセパラブルフラスコに、4-ヒドロキシブチルアクリレートグリシジルエーテル200.23g(1.00mol)、GBL691gを仕込み、室温で撹拌溶解した。更に攪拌しながら3-メルカプト-1,2,4-トリアゾール96.07g(0.95mol)を添加した。次いでオイルバスにて溶液を60℃まで加熱し、更に60℃で6時間反応を行い、化合物(C-2)の30%GBL溶液を得た。 <Synthesis of compound (C-2)>
A separable flask equipped with a stirrer was charged with 200.23 g (1.00 mol) of 4-hydroxybutyl acrylate glycidyl ether and 691 g of GBL, and dissolved with stirring at room temperature. Further, 96.07 g (0.95 mol) of 3-mercapto-1,2,4-triazole was added while stirring. Then, the solution was heated to 60° C. in an oil bath and further reacted at 60° C. for 6 hours to obtain a 30% GBL solution of compound (C-2).
<化合物(C-3)の合成>
撹拌装置付きのセパラブルフラスコに、アクリル酸(3,4-エポキシシクロヘキシル)メチル182.22g(1.00mol)、GBL820gを仕込み、室温で撹拌溶解した。更に攪拌しながら5-メルカプト-1-フェニル-1H-テトラゾール169.30g(0.95mol)を添加した。次いでオイルバスにて溶液を60℃まで加熱し、更に60℃で6時間反応を行い、化合物(C-3)の30%GBL溶液を得た。 <Synthesis of compound (C-3)>
A separable flask equipped with a stirrer was charged with 182.22 g (1.00 mol) of (3,4-epoxycyclohexyl)methyl acrylate and 820 g of GBL, which were stirred and dissolved at room temperature. Further, 169.30 g (0.95 mol) of 5-mercapto-1-phenyl-1H-tetrazole was added while stirring. Then, the solution was heated to 60° C. in an oil bath and further reacted at 60° C. for 6 hours to obtain a 30% GBL solution of compound (C-3).
撹拌装置付きのセパラブルフラスコに、アクリル酸(3,4-エポキシシクロヘキシル)メチル182.22g(1.00mol)、GBL820gを仕込み、室温で撹拌溶解した。更に攪拌しながら5-メルカプト-1-フェニル-1H-テトラゾール169.30g(0.95mol)を添加した。次いでオイルバスにて溶液を60℃まで加熱し、更に60℃で6時間反応を行い、化合物(C-3)の30%GBL溶液を得た。 <Synthesis of compound (C-3)>
A separable flask equipped with a stirrer was charged with 182.22 g (1.00 mol) of (3,4-epoxycyclohexyl)methyl acrylate and 820 g of GBL, which were stirred and dissolved at room temperature. Further, 169.30 g (0.95 mol) of 5-mercapto-1-phenyl-1H-tetrazole was added while stirring. Then, the solution was heated to 60° C. in an oil bath and further reacted at 60° C. for 6 hours to obtain a 30% GBL solution of compound (C-3).
<化合物(C-4)の合成>
撹拌装置付きのセパラブルフラスコに、2-[4-(2,3-エポキシプロポキシ)フェニル]-2-[4-[1,1-ビス[4-([2,3-エポキシプロポキシ]フェニル)エチル]フェニル]プロパン592.00g(1.00mol)、GBL1580gを仕込み、室温で撹拌溶解した。更に攪拌しながら5-アミノ-1H-テトラゾール85.07g(1.00mol)を添加した。次いでオイルバスにて溶液を60℃まで加熱し、更に60℃で6時間反応を行い、化合物(C-4)の30%GBL溶液を得た。 <Synthesis of compound (C-4)>
2-[4-(2,3-epoxypropoxy)phenyl]-2-[4-[1,1-bis[4-([2,3-epoxypropoxy]phenyl) was added to a separable flask equipped with a stirrer. 592.00 g (1.00 mol) of ethyl]phenyl]propane and 1580 g of GBL were charged and dissolved with stirring at room temperature. Further, 85.07 g (1.00 mol) of 5-amino-1H-tetrazole was added while stirring. Then, the solution was heated to 60° C. in an oil bath and further reacted at 60° C. for 6 hours to obtain a 30% GBL solution of compound (C-4).
撹拌装置付きのセパラブルフラスコに、2-[4-(2,3-エポキシプロポキシ)フェニル]-2-[4-[1,1-ビス[4-([2,3-エポキシプロポキシ]フェニル)エチル]フェニル]プロパン592.00g(1.00mol)、GBL1580gを仕込み、室温で撹拌溶解した。更に攪拌しながら5-アミノ-1H-テトラゾール85.07g(1.00mol)を添加した。次いでオイルバスにて溶液を60℃まで加熱し、更に60℃で6時間反応を行い、化合物(C-4)の30%GBL溶液を得た。 <Synthesis of compound (C-4)>
2-[4-(2,3-epoxypropoxy)phenyl]-2-[4-[1,1-bis[4-([2,3-epoxypropoxy]phenyl) was added to a separable flask equipped with a stirrer. 592.00 g (1.00 mol) of ethyl]phenyl]propane and 1580 g of GBL were charged and dissolved with stirring at room temperature. Further, 85.07 g (1.00 mol) of 5-amino-1H-tetrazole was added while stirring. Then, the solution was heated to 60° C. in an oil bath and further reacted at 60° C. for 6 hours to obtain a 30% GBL solution of compound (C-4).
<硬化触媒(H-1)の合成>
撹拌装置付きのセパラブルフラスコに、4,4'-ビスフェノールS37.5g(0.15mol)、メタノール100mLを仕込み、室温で撹拌溶解し、更に攪拌しながら予め50mLのメタノールに水酸化ナトリウム4.0g(0.1mol)を溶解した溶液を添加した。次いで予め150mLのメタノールにテトラフェニルホスホニウムブロマイド41.9g(0.1mol)を溶解した溶液を加えた。しばらく攪拌を継続し、300mLのメタノールを追加した後、フラスコ内の溶液を大量の水に撹拌しながら滴下し、白色沈殿を得た。沈殿を濾過、乾燥し白色結晶の硬化触媒(H-1)を得た。 <Synthesis of Curing Catalyst (H-1)>
A separable flask equipped with a stirrer was charged with 37.5 g (0.15 mol) of 4,4'-bisphenol S and 100 mL of methanol, and dissolved with stirring at room temperature. (0.1 mol) was added. Then, a solution in which 41.9 g (0.1 mol) of tetraphenylphosphonium bromide was previously dissolved in 150 mL of methanol was added. After continuing stirring for a while and adding 300 mL of methanol, the solution in the flask was added dropwise to a large amount of water while stirring to obtain a white precipitate. The precipitate was filtered and dried to obtain a white crystalline curing catalyst (H-1).
撹拌装置付きのセパラブルフラスコに、4,4'-ビスフェノールS37.5g(0.15mol)、メタノール100mLを仕込み、室温で撹拌溶解し、更に攪拌しながら予め50mLのメタノールに水酸化ナトリウム4.0g(0.1mol)を溶解した溶液を添加した。次いで予め150mLのメタノールにテトラフェニルホスホニウムブロマイド41.9g(0.1mol)を溶解した溶液を加えた。しばらく攪拌を継続し、300mLのメタノールを追加した後、フラスコ内の溶液を大量の水に撹拌しながら滴下し、白色沈殿を得た。沈殿を濾過、乾燥し白色結晶の硬化触媒(H-1)を得た。 <Synthesis of Curing Catalyst (H-1)>
A separable flask equipped with a stirrer was charged with 37.5 g (0.15 mol) of 4,4'-bisphenol S and 100 mL of methanol, and dissolved with stirring at room temperature. (0.1 mol) was added. Then, a solution in which 41.9 g (0.1 mol) of tetraphenylphosphonium bromide was previously dissolved in 150 mL of methanol was added. After continuing stirring for a while and adding 300 mL of methanol, the solution in the flask was added dropwise to a large amount of water while stirring to obtain a white precipitate. The precipitate was filtered and dried to obtain a white crystalline curing catalyst (H-1).
[感光性樹脂組成物の調製]
後掲の表1に従い各原料を配合し、室温下で原料が完全に溶解するまで撹拌し、溶液を得た。その後、その溶液を孔径0.2μmのナイロンフィルターで濾過した。このようにして、ワニス状の感光性樹脂組成物を得た。 [Preparation of photosensitive resin composition]
Each raw material was blended according to Table 1 shown later and stirred at room temperature until the raw material was completely dissolved to obtain a solution. The solution was then filtered through a nylon filter with a pore size of 0.2 μm. Thus, a varnish-like photosensitive resin composition was obtained.
後掲の表1に従い各原料を配合し、室温下で原料が完全に溶解するまで撹拌し、溶液を得た。その後、その溶液を孔径0.2μmのナイロンフィルターで濾過した。このようにして、ワニス状の感光性樹脂組成物を得た。 [Preparation of photosensitive resin composition]
Each raw material was blended according to Table 1 shown later and stirred at room temperature until the raw material was completely dissolved to obtain a solution. The solution was then filtered through a nylon filter with a pore size of 0.2 μm. Thus, a varnish-like photosensitive resin composition was obtained.
表1における各成分の原料の詳細は下記のとおりである。
The details of the raw materials for each component in Table 1 are as follows.
樹脂(A)
(A-1)上記で合成した樹脂(イミド環構造含有ポリイミド樹脂)
(A-2)上記で合成した樹脂(ポリアミド酸エステル樹脂) Resin (A)
(A-1) Resin synthesized above (imide ring structure-containing polyimide resin)
(A-2) Resin synthesized above (polyamide acid ester resin)
(A-1)上記で合成した樹脂(イミド環構造含有ポリイミド樹脂)
(A-2)上記で合成した樹脂(ポリアミド酸エステル樹脂) Resin (A)
(A-1) Resin synthesized above (imide ring structure-containing polyimide resin)
(A-2) Resin synthesized above (polyamide acid ester resin)
化合物(C)
(C-1)上記で合成した化合物(メタクリレート基とテトラゾール基を有する化合物)
(C-2)上記で合成した化合物(アクリレート基とトリアゾール基を有する化合物)
(C-3)上記で合成した化合物(アクリレート基とテトラゾール基を有する化合物)
(C-4)上記で合成した化合物(エポキシ基とテトラゾール環を有する化合物) Compound (C)
(C-1) Compound synthesized above (compound having methacrylate group and tetrazole group)
(C-2) Compound synthesized above (compound having acrylate group and triazole group)
(C-3) Compound synthesized above (compound having acrylate group and tetrazole group)
(C-4) Compound synthesized above (compound having epoxy group and tetrazole ring)
(C-1)上記で合成した化合物(メタクリレート基とテトラゾール基を有する化合物)
(C-2)上記で合成した化合物(アクリレート基とトリアゾール基を有する化合物)
(C-3)上記で合成した化合物(アクリレート基とテトラゾール基を有する化合物)
(C-4)上記で合成した化合物(エポキシ基とテトラゾール環を有する化合物) Compound (C)
(C-1) Compound synthesized above (compound having methacrylate group and tetrazole group)
(C-2) Compound synthesized above (compound having acrylate group and triazole group)
(C-3) Compound synthesized above (compound having acrylate group and tetrazole group)
(C-4) Compound synthesized above (compound having epoxy group and tetrazole ring)
多官能(メタ)アクリル化合物
(D-1)ビスコート#802(大阪有機工業(株)製、多官能アクリル化合物)
(D-2)A―9550(新中村化学(株)製、多官能アクリル化合物)
(D-3)ビスコート#300(大阪有機工業(株)製、多官能アクリル化合物)
(D-4)ビスコート#230(大阪有機工業(株)製、多官能アクリル化合物) Polyfunctional (meth) acrylic compound (D-1) Viscoat #802 (manufactured by Osaka Organic Industry Co., Ltd., polyfunctional acrylic compound)
(D-2) A-9550 (manufactured by Shin-Nakamura Chemical Co., Ltd., polyfunctional acrylic compound)
(D-3) Viscoat #300 (manufactured by Osaka Organic Industry Co., Ltd., polyfunctional acrylic compound)
(D-4) Viscoat #230 (manufactured by Osaka Organic Industry Co., Ltd., polyfunctional acrylic compound)
(D-1)ビスコート#802(大阪有機工業(株)製、多官能アクリル化合物)
(D-2)A―9550(新中村化学(株)製、多官能アクリル化合物)
(D-3)ビスコート#300(大阪有機工業(株)製、多官能アクリル化合物)
(D-4)ビスコート#230(大阪有機工業(株)製、多官能アクリル化合物) Polyfunctional (meth) acrylic compound (D-1) Viscoat #802 (manufactured by Osaka Organic Industry Co., Ltd., polyfunctional acrylic compound)
(D-2) A-9550 (manufactured by Shin-Nakamura Chemical Co., Ltd., polyfunctional acrylic compound)
(D-3) Viscoat #300 (manufactured by Osaka Organic Industry Co., Ltd., polyfunctional acrylic compound)
(D-4) Viscoat #230 (manufactured by Osaka Organic Industry Co., Ltd., polyfunctional acrylic compound)
感光剤
(E-1)Irugacure OXE02(BASF社製、オキシムエステル型光ラジカル発生剤) Photosensitive agent (E-1) Irugacure OXE02 (manufactured by BASF, oxime ester type photoradical generator)
(E-1)Irugacure OXE02(BASF社製、オキシムエステル型光ラジカル発生剤) Photosensitive agent (E-1) Irugacure OXE02 (manufactured by BASF, oxime ester type photoradical generator)
熱ラジカル開始剤
(F-1)パーカドックスBC(化薬ヌーリオン(株)製) Thermal radical initiator (F-1) Perkadox BC (manufactured by Kayaku Nourion Co., Ltd.)
(F-1)パーカドックスBC(化薬ヌーリオン(株)製) Thermal radical initiator (F-1) Perkadox BC (manufactured by Kayaku Nourion Co., Ltd.)
エポキシ樹脂
(G-1)EXA-830CRP(DIC(株)、エポキシ樹脂) Epoxy resin (G-1) EXA-830CRP (DIC Corporation, epoxy resin)
(G-1)EXA-830CRP(DIC(株)、エポキシ樹脂) Epoxy resin (G-1) EXA-830CRP (DIC Corporation, epoxy resin)
硬化触媒
(H-1)上記で合成した硬化触媒(ホスホニウム塩) Curing catalyst (H-1) Curing catalyst synthesized above (phosphonium salt)
(H-1)上記で合成した硬化触媒(ホスホニウム塩) Curing catalyst (H-1) Curing catalyst synthesized above (phosphonium salt)
シランカップリング剤
(J-1)X-12-967C(信越化学工業(株)製)
(J-2)KBM-503(信越化学工業(株)製) Silane coupling agent (J-1) X-12-967C (manufactured by Shin-Etsu Chemical Co., Ltd.)
(J-2) KBM-503 (manufactured by Shin-Etsu Chemical Co., Ltd.)
(J-1)X-12-967C(信越化学工業(株)製)
(J-2)KBM-503(信越化学工業(株)製) Silane coupling agent (J-1) X-12-967C (manufactured by Shin-Etsu Chemical Co., Ltd.)
(J-2) KBM-503 (manufactured by Shin-Etsu Chemical Co., Ltd.)
界面活性剤
(K-1)FC4432(3M社製、フッ素系) Surfactant (K-1) FC4432 (manufactured by 3M, fluorine-based)
(K-1)FC4432(3M社製、フッ素系) Surfactant (K-1) FC4432 (manufactured by 3M, fluorine-based)
溶剤
(L-1)乳酸エチル(EL)
(L-2)ガンマ-ブチロラクトン(GBL) Solvent (L-1) ethyl lactate (EL)
(L-2) gamma-butyrolactone (GBL)
(L-1)乳酸エチル(EL)
(L-2)ガンマ-ブチロラクトン(GBL) Solvent (L-1) ethyl lactate (EL)
(L-2) gamma-butyrolactone (GBL)
水
(M-1)イオン交換水 Water (M-1) ion-exchanged water
(M-1)イオン交換水 Water (M-1) ion-exchanged water
[密着性:テープテスト]
<テープテスト用基板の作成>
感光性樹脂組成物を、表面に3000Åのメッキ銅層を有した12インチシリコンウェハ上に、乾燥後の膜厚が10μmとなるようにスピンコートにて塗布し、続いて120℃で3分間加熱することで、感光性樹脂膜を得た。
得られた感光性樹脂膜に、i線ステッパーにて、フォトマスクを介さずに300mJ/cm2の露光を行った。その後、露光された樹脂膜をシリコンウェハごとスプレー現像機にて、シクロペンタノンおよびプロピレングリコールモノメチルエーテルアセテートを用いて、現像した。続いて、スピンドライにて風乾し、120℃で2分間、ホットプレート上で乾燥を行った。さらにその後、窒素雰囲気下、200℃で90分間熱処理した。以上により、テープテスト用基板を得た。 [Adhesion: tape test]
<Preparation of substrate for tape test>
The photosensitive resin composition was applied to a 12-inch silicon wafer having a plated copper layer of 3000 Å on the surface by spin coating so that the film thickness after drying was 10 μm, followed by heating at 120° C. for 3 minutes. By doing so, a photosensitive resin film was obtained.
The resulting photosensitive resin film was exposed to light at 300 mJ/cm 2 using an i-line stepper without a photomask. Thereafter, the exposed resin film was developed together with the silicon wafer using cyclopentanone and propylene glycol monomethyl ether acetate using a spray developer. Subsequently, it was air-dried by spin drying and dried on a hot plate at 120° C. for 2 minutes. After that, heat treatment was performed at 200° C. for 90 minutes in a nitrogen atmosphere. Thus, a substrate for tape test was obtained.
<テープテスト用基板の作成>
感光性樹脂組成物を、表面に3000Åのメッキ銅層を有した12インチシリコンウェハ上に、乾燥後の膜厚が10μmとなるようにスピンコートにて塗布し、続いて120℃で3分間加熱することで、感光性樹脂膜を得た。
得られた感光性樹脂膜に、i線ステッパーにて、フォトマスクを介さずに300mJ/cm2の露光を行った。その後、露光された樹脂膜をシリコンウェハごとスプレー現像機にて、シクロペンタノンおよびプロピレングリコールモノメチルエーテルアセテートを用いて、現像した。続いて、スピンドライにて風乾し、120℃で2分間、ホットプレート上で乾燥を行った。さらにその後、窒素雰囲気下、200℃で90分間熱処理した。以上により、テープテスト用基板を得た。 [Adhesion: tape test]
<Preparation of substrate for tape test>
The photosensitive resin composition was applied to a 12-inch silicon wafer having a plated copper layer of 3000 Å on the surface by spin coating so that the film thickness after drying was 10 μm, followed by heating at 120° C. for 3 minutes. By doing so, a photosensitive resin film was obtained.
The resulting photosensitive resin film was exposed to light at 300 mJ/cm 2 using an i-line stepper without a photomask. Thereafter, the exposed resin film was developed together with the silicon wafer using cyclopentanone and propylene glycol monomethyl ether acetate using a spray developer. Subsequently, it was air-dried by spin drying and dried on a hot plate at 120° C. for 2 minutes. After that, heat treatment was performed at 200° C. for 90 minutes in a nitrogen atmosphere. Thus, a substrate for tape test was obtained.
<テープテスト>
テープテスト用基板の作成にて得られた基板上のフィルムに、カッターを用いて1mm×1mmのパターンを100個作成した。次いで、かかるパターンの表面に対し、剥離強度が3.0mN/10mmのセロテープ(登録商標)を貼り付けた後に、セロテープ(登録商標)を垂直に剥がした。次いで、剥離したパターンの数を数えた。なお、本評価においては、パターンの剥離数が少ないほど銅への密着性が良好であると評価した。 <Tape test>
Using a cutter, 100 patterns of 1 mm×1 mm were formed on the film on the substrate obtained in the preparation of the tape test substrate. Next, after affixing Cellotape (registered trademark) with a peel strength of 3.0 mN/10 mm to the surface of the pattern, Cellotape (registered trademark) was peeled off vertically. Then, the number of peeled patterns was counted. In this evaluation, it was evaluated that the adhesion to copper was better as the number of peeled patterns was smaller.
テープテスト用基板の作成にて得られた基板上のフィルムに、カッターを用いて1mm×1mmのパターンを100個作成した。次いで、かかるパターンの表面に対し、剥離強度が3.0mN/10mmのセロテープ(登録商標)を貼り付けた後に、セロテープ(登録商標)を垂直に剥がした。次いで、剥離したパターンの数を数えた。なお、本評価においては、パターンの剥離数が少ないほど銅への密着性が良好であると評価した。 <Tape test>
Using a cutter, 100 patterns of 1 mm×1 mm were formed on the film on the substrate obtained in the preparation of the tape test substrate. Next, after affixing Cellotape (registered trademark) with a peel strength of 3.0 mN/10 mm to the surface of the pattern, Cellotape (registered trademark) was peeled off vertically. Then, the number of peeled patterns was counted. In this evaluation, it was evaluated that the adhesion to copper was better as the number of peeled patterns was smaller.
[密着性:90度ピール強度]
<90度ピール強度評価用基板の作成>
感光性樹脂組成物を、表面に3000Åのメッキ銅層を有した12インチシリコンウェハ上に、乾燥後の膜厚が10μmとなるようにスピンコートにて塗布し、続いて120℃で3分間加熱することで、感光性樹脂膜を得た。
得られた感光性樹脂膜に、i線ステッパーにて、幅6.5mm、長さ50mmの範囲が露光されるようにフォトマスクを介して、300mJ/cm2の露光を行った。その後、露光された樹脂膜をシリコンウェハごとスプレー現像機にて、シクロペンタノンおよびプロピレングリコールモノメチルエーテルアセテートを用いて、現像した。続いて、スピンドライにて風乾後、120℃で2分間、ホットプレート上で乾燥を行った。さらにその後、窒素雰囲気下、200℃で90分間熱処理し、硬化膜を得た。
続いて、得られた幅6.5mm、長さ50mmの硬化膜が残るようにシリコンウェハをカットし、硬化膜の端部(5mm)をCuエッチング液に23℃で24時間浸漬後、水洗・乾燥し、端部のフィルムが剥離した90度ピール強度評価用基板を得た。 [Adhesion: 90 degree peel strength]
<Preparation of substrate for 90 degree peel strength evaluation>
The photosensitive resin composition was applied to a 12-inch silicon wafer having a plated copper layer of 3000 Å on the surface by spin coating so that the film thickness after drying was 10 μm, followed by heating at 120° C. for 3 minutes. By doing so, a photosensitive resin film was obtained.
The resulting photosensitive resin film was exposed to light of 300 mJ/cm 2 with an i-line stepper through a photomask so that a range of 6.5 mm in width and 50 mm in length was exposed. Thereafter, the exposed resin film was developed together with the silicon wafer using cyclopentanone and propylene glycol monomethyl ether acetate using a spray developer. Subsequently, after air-drying by spin drying, drying was performed on a hot plate at 120° C. for 2 minutes. After that, heat treatment was performed at 200° C. for 90 minutes in a nitrogen atmosphere to obtain a cured film.
Subsequently, the silicon wafer was cut so that a cured film having a width of 6.5 mm and a length of 50 mm remained. After drying, a substrate for 90-degree peel strength evaluation was obtained from which the film at the edge was peeled off.
<90度ピール強度評価用基板の作成>
感光性樹脂組成物を、表面に3000Åのメッキ銅層を有した12インチシリコンウェハ上に、乾燥後の膜厚が10μmとなるようにスピンコートにて塗布し、続いて120℃で3分間加熱することで、感光性樹脂膜を得た。
得られた感光性樹脂膜に、i線ステッパーにて、幅6.5mm、長さ50mmの範囲が露光されるようにフォトマスクを介して、300mJ/cm2の露光を行った。その後、露光された樹脂膜をシリコンウェハごとスプレー現像機にて、シクロペンタノンおよびプロピレングリコールモノメチルエーテルアセテートを用いて、現像した。続いて、スピンドライにて風乾後、120℃で2分間、ホットプレート上で乾燥を行った。さらにその後、窒素雰囲気下、200℃で90分間熱処理し、硬化膜を得た。
続いて、得られた幅6.5mm、長さ50mmの硬化膜が残るようにシリコンウェハをカットし、硬化膜の端部(5mm)をCuエッチング液に23℃で24時間浸漬後、水洗・乾燥し、端部のフィルムが剥離した90度ピール強度評価用基板を得た。 [Adhesion: 90 degree peel strength]
<Preparation of substrate for 90 degree peel strength evaluation>
The photosensitive resin composition was applied to a 12-inch silicon wafer having a plated copper layer of 3000 Å on the surface by spin coating so that the film thickness after drying was 10 μm, followed by heating at 120° C. for 3 minutes. By doing so, a photosensitive resin film was obtained.
The resulting photosensitive resin film was exposed to light of 300 mJ/cm 2 with an i-line stepper through a photomask so that a range of 6.5 mm in width and 50 mm in length was exposed. Thereafter, the exposed resin film was developed together with the silicon wafer using cyclopentanone and propylene glycol monomethyl ether acetate using a spray developer. Subsequently, after air-drying by spin drying, drying was performed on a hot plate at 120° C. for 2 minutes. After that, heat treatment was performed at 200° C. for 90 minutes in a nitrogen atmosphere to obtain a cured film.
Subsequently, the silicon wafer was cut so that a cured film having a width of 6.5 mm and a length of 50 mm remained. After drying, a substrate for 90-degree peel strength evaluation was obtained from which the film at the edge was peeled off.
<90度ピール強度>
90度ピール強度評価用基板の作成にて得られた基板について、90度ピール強度測定装置(島津製作所(株)製、AUTOGRAPH AG-Xplus)にセットし、剥離速度20mm/分にて1cm剥離を行い、剥離強度の平均値を評価した。90度ピール強度の単位はN/cmである。90度ピール強度は信頼性の面から高い方が好ましい。 <90 degree peel strength>
The substrate obtained in the preparation of the 90-degree peel strength evaluation substrate is set in a 90-degree peel strength measuring device (manufactured by Shimadzu Corporation, AUTOGRAPH AG-Xplus), and 1 cm is peeled at a peeling speed of 20 mm / min. and evaluated the average value of the peel strength. The unit of 90 degree peel strength is N/cm. A higher 90-degree peel strength is preferable from the standpoint of reliability.
90度ピール強度評価用基板の作成にて得られた基板について、90度ピール強度測定装置(島津製作所(株)製、AUTOGRAPH AG-Xplus)にセットし、剥離速度20mm/分にて1cm剥離を行い、剥離強度の平均値を評価した。90度ピール強度の単位はN/cmである。90度ピール強度は信頼性の面から高い方が好ましい。 <90 degree peel strength>
The substrate obtained in the preparation of the 90-degree peel strength evaluation substrate is set in a 90-degree peel strength measuring device (manufactured by Shimadzu Corporation, AUTOGRAPH AG-Xplus), and 1 cm is peeled at a peeling speed of 20 mm / min. and evaluated the average value of the peel strength. The unit of 90 degree peel strength is N/cm. A higher 90-degree peel strength is preferable from the standpoint of reliability.
[耐熱性:ガラス転移温度]
<ガラス転移温度測定用試験片の作成>
上記<90度ピール強度評価用基板の作成>と同様の方法で得られた感光性樹脂膜に、i線ステッパーにて幅5mm、長さ50mmの範囲が露光されるようにフォトマスクを介して300mJ/cm2の露光を行った。その後、露光された樹脂膜をシリコンウェハごとスプレー現像機にて、シクロペンタノンおよびプロピレングリコールモノメチルエーテルアセテートを用いて、現像した。続いて、スピンドライにて風乾後、120℃で、2分間ホットプレート上で乾燥を行った。さらにその後、窒素雰囲気下、200℃で90分間熱処理し、硬化膜を得た。
得られた硬化物を2質量%フッ酸水溶液中に浸漬することで基板より剥離し、水洗後、60℃で10時間乾燥して、試験片(50mm×5mm×10μm厚)を得た。 [Heat resistance: glass transition temperature]
<Preparation of test piece for glass transition temperature measurement>
A photosensitive resin film obtained in the same manner as in <Preparation of substrate for 90 degree peel strength evaluation> above is exposed through a photomask so that a range of 5 mm in width and 50 mm in length is exposed using an i-line stepper. Exposure was performed at 300 mJ/cm 2 . Thereafter, the exposed resin film was developed together with the silicon wafer using cyclopentanone and propylene glycol monomethyl ether acetate using a spray developer. Subsequently, after air-drying by spin drying, drying was performed on a hot plate at 120° C. for 2 minutes. After that, heat treatment was performed at 200° C. for 90 minutes in a nitrogen atmosphere to obtain a cured film.
The resulting cured product was immersed in a 2% by mass hydrofluoric acid aqueous solution to separate from the substrate, washed with water, and dried at 60° C. for 10 hours to obtain a test piece (50 mm×5 mm×10 μm thick).
<ガラス転移温度測定用試験片の作成>
上記<90度ピール強度評価用基板の作成>と同様の方法で得られた感光性樹脂膜に、i線ステッパーにて幅5mm、長さ50mmの範囲が露光されるようにフォトマスクを介して300mJ/cm2の露光を行った。その後、露光された樹脂膜をシリコンウェハごとスプレー現像機にて、シクロペンタノンおよびプロピレングリコールモノメチルエーテルアセテートを用いて、現像した。続いて、スピンドライにて風乾後、120℃で、2分間ホットプレート上で乾燥を行った。さらにその後、窒素雰囲気下、200℃で90分間熱処理し、硬化膜を得た。
得られた硬化物を2質量%フッ酸水溶液中に浸漬することで基板より剥離し、水洗後、60℃で10時間乾燥して、試験片(50mm×5mm×10μm厚)を得た。 [Heat resistance: glass transition temperature]
<Preparation of test piece for glass transition temperature measurement>
A photosensitive resin film obtained in the same manner as in <Preparation of substrate for 90 degree peel strength evaluation> above is exposed through a photomask so that a range of 5 mm in width and 50 mm in length is exposed using an i-line stepper. Exposure was performed at 300 mJ/cm 2 . Thereafter, the exposed resin film was developed together with the silicon wafer using cyclopentanone and propylene glycol monomethyl ether acetate using a spray developer. Subsequently, after air-drying by spin drying, drying was performed on a hot plate at 120° C. for 2 minutes. After that, heat treatment was performed at 200° C. for 90 minutes in a nitrogen atmosphere to obtain a cured film.
The resulting cured product was immersed in a 2% by mass hydrofluoric acid aqueous solution to separate from the substrate, washed with water, and dried at 60° C. for 10 hours to obtain a test piece (50 mm×5 mm×10 μm thick).
<ガラス転移温度の測定>
熱機械分析装置(セイコーインスツルメンツ社製、TMA/SS6000)を用いて、得られた試験片を、10℃/分の昇温速度で300℃まで加熱し、得られた試験片の熱膨張率を測定した。
次いで、得られた測定結果に基づき、熱膨張率の変曲点から硬化物のガラス転移温度(Tg)を算出した。Tgの単位は、℃である。熱膨張率に変曲点が観察されなかったものについては、Tg>300℃として評価した。 <Measurement of glass transition temperature>
Using a thermomechanical analyzer (manufactured by Seiko Instruments Inc., TMA/SS6000), the obtained test piece was heated to 300 ° C. at a heating rate of 10 ° C./min, and the thermal expansion coefficient of the obtained test piece was measured. It was measured.
Next, based on the obtained measurement results, the glass transition temperature (Tg) of the cured product was calculated from the inflection point of the coefficient of thermal expansion. The unit of Tg is °C. Those for which no inflection point was observed in the coefficient of thermal expansion were evaluated as Tg>300°C.
熱機械分析装置(セイコーインスツルメンツ社製、TMA/SS6000)を用いて、得られた試験片を、10℃/分の昇温速度で300℃まで加熱し、得られた試験片の熱膨張率を測定した。
次いで、得られた測定結果に基づき、熱膨張率の変曲点から硬化物のガラス転移温度(Tg)を算出した。Tgの単位は、℃である。熱膨張率に変曲点が観察されなかったものについては、Tg>300℃として評価した。 <Measurement of glass transition temperature>
Using a thermomechanical analyzer (manufactured by Seiko Instruments Inc., TMA/SS6000), the obtained test piece was heated to 300 ° C. at a heating rate of 10 ° C./min, and the thermal expansion coefficient of the obtained test piece was measured. It was measured.
Next, based on the obtained measurement results, the glass transition temperature (Tg) of the cured product was calculated from the inflection point of the coefficient of thermal expansion. The unit of Tg is °C. Those for which no inflection point was observed in the coefficient of thermal expansion were evaluated as Tg>300°C.
[引張り伸び率]
まず、上記<ガラス転移温度(Tg)の測定>と同様にして試験片を作成した。
得られた試験片について、引張試験機(オリエンテック社製、テンシロンRTC-1210A)を用い、23℃雰囲気下、JIS K 7161に準拠した方法で引張試験を実施し、試験片の引張伸び率を測定した。引張試験における延伸速度は、5mm/分とした。引張伸び率の単位は、%である。 [Tensile elongation]
First, a test piece was prepared in the same manner as in <Measurement of glass transition temperature (Tg)>.
The resulting test piece was subjected to a tensile test using a tensile tester (Tensilon RTC-1210A, manufactured by Orientec Co., Ltd.) in an atmosphere of 23° C. in accordance with JIS K 7161, and the tensile elongation of the test piece was measured. It was measured. The drawing speed in the tensile test was 5 mm/min. The unit of tensile elongation is %.
まず、上記<ガラス転移温度(Tg)の測定>と同様にして試験片を作成した。
得られた試験片について、引張試験機(オリエンテック社製、テンシロンRTC-1210A)を用い、23℃雰囲気下、JIS K 7161に準拠した方法で引張試験を実施し、試験片の引張伸び率を測定した。引張試験における延伸速度は、5mm/分とした。引張伸び率の単位は、%である。 [Tensile elongation]
First, a test piece was prepared in the same manner as in <Measurement of glass transition temperature (Tg)>.
The resulting test piece was subjected to a tensile test using a tensile tester (Tensilon RTC-1210A, manufactured by Orientec Co., Ltd.) in an atmosphere of 23° C. in accordance with JIS K 7161, and the tensile elongation of the test piece was measured. It was measured. The drawing speed in the tensile test was 5 mm/min. The unit of tensile elongation is %.
[パターニング性]
感光性樹脂組成物を、表面に3000Åのメッキ銅層を有した12インチシリコンウェハ上に、乾燥後の膜厚が5μmとなるようにスピンコートし、ホットプレートにて100℃で3分間乾燥し、感光性樹脂膜を得た。この感光性樹脂膜に、凸版印刷社製マスク(テストチャートNo.1:幅0.5~50μmの残しパターンおよび抜きパターンが描かれている)を通して、i線ステッパー(ニコン社製、NSR-4425i)を用いて、露光量を変化させながらi線を照射した。
スプレー現像機にて、シクロペンタノンを用いて2500回転で30秒、続いてプロピレングリコールモノメチルエーテルアセテートを用いて2500回転で10秒現像した。更に2500回転で10秒スピンドライにて風乾後、ホットプレート上120℃で2分間の乾燥を行った。さらにその後、窒素雰囲気下、200℃で90分間熱処理し、パターン付きの硬化膜を得た。
得られたパターンについて観察し、7μmΦのビアホールが開口したものを◎(とても良い)、10μmΦのビアホールが開口したものを○(良い)、10μmのビアホールが開口しなかったものを×(悪い)として評価した。 [Patternability]
The photosensitive resin composition was spin-coated on a 12-inch silicon wafer having a plated copper layer of 3000 Å on the surface so that the film thickness after drying was 5 μm, and dried on a hot plate at 100° C. for 3 minutes. , to obtain a photosensitive resin film. This photosensitive resin film is passed through a Toppan Printing Co., Ltd. mask (test chart No. 1: a left pattern and a blank pattern with a width of 0.5 to 50 μm are drawn), an i-line stepper (NSR-4425i manufactured by Nikon Corporation). ) was used to irradiate the i-line while changing the exposure amount.
Using a spray developing machine, the film was developed with cyclopentanone at 2500 rpm for 30 seconds, and then with propylene glycol monomethyl ether acetate at 2500 rpm for 10 seconds. Further, after air-drying by spin drying at 2500 rpm for 10 seconds, drying was performed on a hot plate at 120° C. for 2 minutes. After that, heat treatment was performed at 200° C. for 90 minutes in a nitrogen atmosphere to obtain a patterned cured film.
The obtained pattern was observed, and the pattern with a via hole of 7 μmΦ was evaluated as ◎ (very good), the pattern with a via hole with a diameter of 10 μm was evaluated as ○ (good), and the pattern with a via hole with a diameter of 10 μm was evaluated as × (bad). evaluated.
感光性樹脂組成物を、表面に3000Åのメッキ銅層を有した12インチシリコンウェハ上に、乾燥後の膜厚が5μmとなるようにスピンコートし、ホットプレートにて100℃で3分間乾燥し、感光性樹脂膜を得た。この感光性樹脂膜に、凸版印刷社製マスク(テストチャートNo.1:幅0.5~50μmの残しパターンおよび抜きパターンが描かれている)を通して、i線ステッパー(ニコン社製、NSR-4425i)を用いて、露光量を変化させながらi線を照射した。
スプレー現像機にて、シクロペンタノンを用いて2500回転で30秒、続いてプロピレングリコールモノメチルエーテルアセテートを用いて2500回転で10秒現像した。更に2500回転で10秒スピンドライにて風乾後、ホットプレート上120℃で2分間の乾燥を行った。さらにその後、窒素雰囲気下、200℃で90分間熱処理し、パターン付きの硬化膜を得た。
得られたパターンについて観察し、7μmΦのビアホールが開口したものを◎(とても良い)、10μmΦのビアホールが開口したものを○(良い)、10μmのビアホールが開口しなかったものを×(悪い)として評価した。 [Patternability]
The photosensitive resin composition was spin-coated on a 12-inch silicon wafer having a plated copper layer of 3000 Å on the surface so that the film thickness after drying was 5 μm, and dried on a hot plate at 100° C. for 3 minutes. , to obtain a photosensitive resin film. This photosensitive resin film is passed through a Toppan Printing Co., Ltd. mask (test chart No. 1: a left pattern and a blank pattern with a width of 0.5 to 50 μm are drawn), an i-line stepper (NSR-4425i manufactured by Nikon Corporation). ) was used to irradiate the i-line while changing the exposure amount.
Using a spray developing machine, the film was developed with cyclopentanone at 2500 rpm for 30 seconds, and then with propylene glycol monomethyl ether acetate at 2500 rpm for 10 seconds. Further, after air-drying by spin drying at 2500 rpm for 10 seconds, drying was performed on a hot plate at 120° C. for 2 minutes. After that, heat treatment was performed at 200° C. for 90 minutes in a nitrogen atmosphere to obtain a patterned cured film.
The obtained pattern was observed, and the pattern with a via hole of 7 μmΦ was evaluated as ◎ (very good), the pattern with a via hole with a diameter of 10 μm was evaluated as ○ (good), and the pattern with a via hole with a diameter of 10 μm was evaluated as × (bad). evaluated.
[常温粘度変化率]
配合直後の感光性樹脂組成物の粘度を、E型粘度計(TVE-25L)にて測定した。この時の粘度をAとした。その後、感光性樹脂組成物のワニスを23℃にて7日間保管を行い、再度粘度を測定した。この時の粘度をBとした。
粘度Aおよび粘度Bを下記式に代入して、粘度変化率を算出した。粘度変化率が5%以下のものを◎(とても良い)、5%超え10%以下のものを○(良い)、10%を超えたものを×(悪い)として評価した。粘度変化率は、安定した膜厚を得るために、低いほうが好ましい。
粘度変化率[%]={(粘度A-粘度B)/粘度A}×100 [Room temperature viscosity change rate]
The viscosity of the photosensitive resin composition immediately after blending was measured with an E-type viscometer (TVE-25L). The viscosity at this time was defined as A. After that, the varnish of the photosensitive resin composition was stored at 23° C. for 7 days, and the viscosity was measured again. The viscosity at this time was defined as B.
The viscosity change rate was calculated by substituting viscosity A and viscosity B into the following formula. A viscosity change rate of 5% or less was evaluated as ⊚ (very good), a viscosity change rate of more than 5% and 10% or less was evaluated as ◯ (good), and a viscosity change rate of more than 10% was evaluated as x (bad). A lower viscosity change rate is preferable in order to obtain a stable film thickness.
Viscosity change rate [%] = {(viscosity A - viscosity B) / viscosity A} x 100
配合直後の感光性樹脂組成物の粘度を、E型粘度計(TVE-25L)にて測定した。この時の粘度をAとした。その後、感光性樹脂組成物のワニスを23℃にて7日間保管を行い、再度粘度を測定した。この時の粘度をBとした。
粘度Aおよび粘度Bを下記式に代入して、粘度変化率を算出した。粘度変化率が5%以下のものを◎(とても良い)、5%超え10%以下のものを○(良い)、10%を超えたものを×(悪い)として評価した。粘度変化率は、安定した膜厚を得るために、低いほうが好ましい。
粘度変化率[%]={(粘度A-粘度B)/粘度A}×100 [Room temperature viscosity change rate]
The viscosity of the photosensitive resin composition immediately after blending was measured with an E-type viscometer (TVE-25L). The viscosity at this time was defined as A. After that, the varnish of the photosensitive resin composition was stored at 23° C. for 7 days, and the viscosity was measured again. The viscosity at this time was defined as B.
The viscosity change rate was calculated by substituting viscosity A and viscosity B into the following formula. A viscosity change rate of 5% or less was evaluated as ⊚ (very good), a viscosity change rate of more than 5% and 10% or less was evaluated as ◯ (good), and a viscosity change rate of more than 10% was evaluated as x (bad). A lower viscosity change rate is preferable in order to obtain a stable film thickness.
Viscosity change rate [%] = {(viscosity A - viscosity B) / viscosity A} x 100
[熱サイクル試験]
<熱サイクル試験用サンプルの作製>
酸化膜付きの12インチシリコンウェハ上に、幅5μm/ピッチ5μm、高さ5μmの櫛歯型のCu配線を形成したCu配線基板を作製した。
感光性樹脂組成物を、上記Cu配線基板上に、スピンコートによって、乾燥後の膜厚(配線がない部分の厚み)が10μmになるように塗布し、120℃で3分乾燥して感光性樹脂膜を形成した。
得られた感光性樹脂膜に、i線ステッパーを用いて、フォトマスクを介さずに300mJ/cm2の露光を行った。その後スプレー現像機にてシクロペンタノンを用いて2500回転で30秒、続いてプロピレングリコールモノメチルエーテルアセテートにて2500回転で10秒現像した。更に2500回転で10秒スピンドライにて風乾後、ホットプレート上120℃で2分間の乾燥を行った。さらにその後、窒素雰囲気下、200℃で90分間熱処理し、熱サイクル試験用サンプルを得た。 [Thermal cycle test]
<Preparation of sample for thermal cycle test>
A Cu wiring substrate was prepared by forming comb-shaped Cu wiring having a width of 5 μm, a pitch of 5 μm, and a height of 5 μm on a 12-inch silicon wafer with an oxide film.
The photosensitive resin composition is applied onto the Cu wiring substrate by spin coating so that the film thickness after drying (the thickness of the portion without wiring) is 10 μm, and dried at 120° C. for 3 minutes to make it photosensitive. A resin film was formed.
The resulting photosensitive resin film was exposed to light at 300 mJ/cm 2 using an i-line stepper without passing through a photomask. Then, it was developed with a spray developing machine using cyclopentanone at 2500 rpm for 30 seconds, and then with propylene glycol monomethyl ether acetate at 2500 rpm for 10 seconds. Further, after air-drying by spin drying at 2500 rpm for 10 seconds, drying was performed on a hot plate at 120° C. for 2 minutes. After that, heat treatment was performed at 200° C. for 90 minutes in a nitrogen atmosphere to obtain a sample for thermal cycle test.
<熱サイクル試験用サンプルの作製>
酸化膜付きの12インチシリコンウェハ上に、幅5μm/ピッチ5μm、高さ5μmの櫛歯型のCu配線を形成したCu配線基板を作製した。
感光性樹脂組成物を、上記Cu配線基板上に、スピンコートによって、乾燥後の膜厚(配線がない部分の厚み)が10μmになるように塗布し、120℃で3分乾燥して感光性樹脂膜を形成した。
得られた感光性樹脂膜に、i線ステッパーを用いて、フォトマスクを介さずに300mJ/cm2の露光を行った。その後スプレー現像機にてシクロペンタノンを用いて2500回転で30秒、続いてプロピレングリコールモノメチルエーテルアセテートにて2500回転で10秒現像した。更に2500回転で10秒スピンドライにて風乾後、ホットプレート上120℃で2分間の乾燥を行った。さらにその後、窒素雰囲気下、200℃で90分間熱処理し、熱サイクル試験用サンプルを得た。 [Thermal cycle test]
<Preparation of sample for thermal cycle test>
A Cu wiring substrate was prepared by forming comb-shaped Cu wiring having a width of 5 μm, a pitch of 5 μm, and a height of 5 μm on a 12-inch silicon wafer with an oxide film.
The photosensitive resin composition is applied onto the Cu wiring substrate by spin coating so that the film thickness after drying (the thickness of the portion without wiring) is 10 μm, and dried at 120° C. for 3 minutes to make it photosensitive. A resin film was formed.
The resulting photosensitive resin film was exposed to light at 300 mJ/cm 2 using an i-line stepper without passing through a photomask. Then, it was developed with a spray developing machine using cyclopentanone at 2500 rpm for 30 seconds, and then with propylene glycol monomethyl ether acetate at 2500 rpm for 10 seconds. Further, after air-drying by spin drying at 2500 rpm for 10 seconds, drying was performed on a hot plate at 120° C. for 2 minutes. After that, heat treatment was performed at 200° C. for 90 minutes in a nitrogen atmosphere to obtain a sample for thermal cycle test.
<熱サイクル試験>
熱サイクル試験用サンプルの作製にて得られた試験サンプルを温度サイクル試験装置(TCT装置)(エスペック製、TSA-72EH-W)にセットし、-60℃から200℃への昇温およびその後の-60℃への降温を1サイクルとして、200サイクルの処理を行った。
続いて、FIB(集束イオンビーム)処理にて、Cu配線部の断面を出し、SEMにて観察した。各実施例および比較例において、それぞれ、合計10か所の配線と樹脂膜の界面を観察した。
10か所すべてで剥離が観察されなかった場合を○(良い)、1か所でも剥離が観察されたものを×(悪い)と評価した。 <Thermal cycle test>
The test sample obtained in the preparation of the thermal cycle test sample is set in a temperature cycle test device (TCT device) (manufactured by Espec, TSA-72EH-W), and the temperature is raised from -60 ° C. to 200 ° C. and then The treatment was performed for 200 cycles, one cycle being a temperature drop to -60°C.
Subsequently, a cross section of the Cu wiring portion was taken out by FIB (focused ion beam) processing and observed by SEM. In each example and comparative example, a total of 10 interfaces between the wiring and the resin film were observed.
When peeling was not observed at all 10 locations, it was evaluated as ◯ (good), and when peeling was observed at even one location, it was evaluated as x (bad).
熱サイクル試験用サンプルの作製にて得られた試験サンプルを温度サイクル試験装置(TCT装置)(エスペック製、TSA-72EH-W)にセットし、-60℃から200℃への昇温およびその後の-60℃への降温を1サイクルとして、200サイクルの処理を行った。
続いて、FIB(集束イオンビーム)処理にて、Cu配線部の断面を出し、SEMにて観察した。各実施例および比較例において、それぞれ、合計10か所の配線と樹脂膜の界面を観察した。
10か所すべてで剥離が観察されなかった場合を○(良い)、1か所でも剥離が観察されたものを×(悪い)と評価した。 <Thermal cycle test>
The test sample obtained in the preparation of the thermal cycle test sample is set in a temperature cycle test device (TCT device) (manufactured by Espec, TSA-72EH-W), and the temperature is raised from -60 ° C. to 200 ° C. and then The treatment was performed for 200 cycles, one cycle being a temperature drop to -60°C.
Subsequently, a cross section of the Cu wiring portion was taken out by FIB (focused ion beam) processing and observed by SEM. In each example and comparative example, a total of 10 interfaces between the wiring and the resin film were observed.
When peeling was not observed at all 10 locations, it was evaluated as ◯ (good), and when peeling was observed at even one location, it was evaluated as x (bad).
表1に示されるとおり、実施例1~7の感光性樹脂組成物は、比較例1と比較して、テープテスト、90°ピール強度および熱サイクル試験の結果がいずれも優れていた。これらの評価結果により、実施例1~7の感光性樹脂組成物は、基板との密着性に優れることが理解される。
As shown in Table 1, the photosensitive resin compositions of Examples 1 to 7 were superior to Comparative Example 1 in all of the tape test, 90° peel strength, and thermal cycle test results. From these evaluation results, it is understood that the photosensitive resin compositions of Examples 1 to 7 are excellent in adhesion to substrates.
この出願は、2021年3月26日に出願された日本出願特願2021-054154号を基礎とする優先権を主張し、その開示の全てをここに取り込む。
This application claims priority based on Japanese Patent Application No. 2021-054154 filed on March 26, 2021, and the entire disclosure thereof is incorporated herein.
Claims (9)
- ポリイミド樹脂およびその前駆体、ポリベンゾオキサゾール樹脂およびその前駆体、ポリアミド樹脂、ノボラック樹脂、ならびにシクロオレフィン樹脂からなる群より選択される少なくとも一種以上の樹脂(A)と、
エポキシ基および(メタ)アクリロイル基からなる群より選択される少なくとも一種以上の反応性基、および5員環の含窒素複素環基を有する化合物(C)と、
を含有することを特徴とする感光性樹脂組成物。 At least one or more resins (A) selected from the group consisting of polyimide resins and their precursors, polybenzoxazole resins and their precursors, polyamide resins, novolak resins, and cycloolefin resins;
a compound (C) having at least one reactive group selected from the group consisting of an epoxy group and a (meth)acryloyl group, and a 5-membered nitrogen-containing heterocyclic group;
A photosensitive resin composition comprising: - 前記化合物(C)が、前記5員環の含窒素複素環基として、トリアゾール基およびテトラゾール基からなる群より選択される少なくとも一種以上の基を有する化合物である、請求項1に記載の感光性樹脂組成物。 The photosensitive compound according to claim 1, wherein the compound (C) is a compound having at least one group selected from the group consisting of a triazole group and a tetrazole group as the five-membered nitrogen-containing heterocyclic group. Resin composition.
- 前記化合物(C)が、分子末端に前記反応性基を有する化合物である、請求項1または2に記載の感光性樹脂組成物。 The photosensitive resin composition according to claim 1 or 2, wherein the compound (C) is a compound having the reactive group at the molecular end.
- 前記化合物(C)として、下記一般式(I)で表される化合物を含む、請求項1~3の何れか一項に記載の感光性樹脂組成物。
R1は、水素原子またはメチル基であり、
R2は、水素原子、ハロゲン原子、炭素原子数1~20である置換もしくは非置換のアルキル基、炭素原子数3~15である置換もしくは非置換のシクロアルキル基、または炭素原子数6~20である置換もしくは非置換の芳香族炭化水素基であり、
Xは、-S-または-NH-であり、
Yは、-CH=または-N=であり、
Aは、-O-(CH2)m-または単結合であり、Aにおけるmは1~10の正の整数であり、
nは1~10の正の整数である。 The photosensitive resin composition according to any one of claims 1 to 3, comprising a compound represented by the following general formula (I) as the compound (C).
R 1 is a hydrogen atom or a methyl group,
R 2 is a hydrogen atom, a halogen atom, a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted cycloalkyl group having 3 to 15 carbon atoms, or 6 to 20 carbon atoms; is a substituted or unsubstituted aromatic hydrocarbon group,
X is -S- or -NH-,
Y is -CH= or -N=,
A is —O—(CH 2 ) m — or a single bond, m in A is a positive integer from 1 to 10,
n is a positive integer from 1 to 10; - 前記一般式(I)において、Xが-S-である、請求項4に記載の感光性樹脂組成物。 The photosensitive resin composition according to claim 4, wherein in the general formula (I), X is -S-.
- さらに、多官能(メタ)アクリル化合物を含む、請求項1~5のいずれか一項に記載の感光性樹脂組成物。 The photosensitive resin composition according to any one of claims 1 to 5, further comprising a polyfunctional (meth)acrylic compound.
- さらに、感光剤を含む、請求項1~6のいずれか一項に記載の感光性樹脂組成物。 The photosensitive resin composition according to any one of claims 1 to 6, further comprising a photosensitizer.
- 請求項1~7の何れか一項に記載の感光性樹脂組成物の硬化物からなる樹脂膜。 A resin film made of a cured product of the photosensitive resin composition according to any one of claims 1 to 7.
- 請求項8に記載の樹脂膜を備える電子装置。 An electronic device comprising the resin film according to claim 8.
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JP2002258485A (en) * | 2001-02-28 | 2002-09-11 | Asahi Kasei Corp | Photosensitive resin composition |
JP2006119513A (en) * | 2004-10-25 | 2006-05-11 | Kaneka Corp | Photosensitive resin composition and photosensitive dry film resist, and printed wiring board using same |
JP2018005186A (en) * | 2016-07-08 | 2018-01-11 | 旭化成株式会社 | Photosensitive resin composition, photosensitive resin laminate, production method of resin pattern, cured film and display device |
JP2020091464A (en) * | 2018-04-27 | 2020-06-11 | 旭化成株式会社 | Negative photosensitive resin composition and production method of the same |
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Publication number | Priority date | Publication date | Assignee | Title |
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JP2002258485A (en) * | 2001-02-28 | 2002-09-11 | Asahi Kasei Corp | Photosensitive resin composition |
JP2006119513A (en) * | 2004-10-25 | 2006-05-11 | Kaneka Corp | Photosensitive resin composition and photosensitive dry film resist, and printed wiring board using same |
JP2018005186A (en) * | 2016-07-08 | 2018-01-11 | 旭化成株式会社 | Photosensitive resin composition, photosensitive resin laminate, production method of resin pattern, cured film and display device |
JP2020091464A (en) * | 2018-04-27 | 2020-06-11 | 旭化成株式会社 | Negative photosensitive resin composition and production method of the same |
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